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| United States Patent |
5,177,147
|
|
Spenadel
, et al.
|
January 5, 1993
|
Elastomer-plastic blends
Abstract
The present invention relates to compositions comprising at least one
elastomer and at least one plastic. The composition can be produced by
preparing the elastomer and then blending it with the plastic. The
composition can be subjected to an additional step of curing.
| Inventors:
|
Spenadel; Lawrence (Westfield, NJ);
Grosser; Joel H. (Perth Amboy, NJ);
Dwyer; Stephen M. (Howell, NJ)
|
| Assignee:
|
Advanced Elastomer Systems, LP (St. Louis, MO)
|
| Appl. No.:
|
570492 |
| Filed:
|
August 21, 1990 |
| Current U.S. Class: |
525/88; 525/86; 525/93; 525/133; 525/155; 525/166; 525/179; 525/193; 525/211; 525/222; 525/227; 525/239; 525/240 |
| Intern'l Class: |
C08L 023/16; C08L 023/26; C08L 023/6; C08L 023/12 |
| Field of Search: |
525/240,211,88,93,133,155,166,179,193,222,227,239
|
References Cited
U.S. Patent Documents
| 3262992 | Jul., 1966 | Holzer et al. | 525/88.
|
| 3468979 | Sep., 1969 | Hamed et al. | 525/240.
|
| 3629212 | Dec., 1971 | Benedikter | 260/8.
|
| 3662548 | Nov., 1971 | Emde et al. | 260/80.
|
| 3697429 | Oct., 1972 | Engel et al. | 525/59.
|
| 3723348 | Mar., 1973 | Apotheker et al. | 252/429.
|
| 3879494 | Apr., 1975 | Milkovitch | 260/876.
|
| 3884993 | May., 1975 | Gros | 260/897.
|
| 3937758 | Feb., 1976 | Castagna | 525/88.
|
| 4059651 | Nov., 1977 | Smith, Jr. | 525/211.
|
| 4087485 | May., 1978 | Huff | 525/240.
|
| 4087486 | May., 1978 | Fielding et al. | 525/240.
|
| 4130535 | Dec., 1978 | Coran et al. | 525/211.
|
| 4168358 | Sep., 1979 | Harada et al. | 526/143.
|
| 4181790 | Jan., 1980 | Maaks et al. | 526/143.
|
| 4221882 | Sep., 1980 | Huff | 525/197.
|
| 4251646 | Feb., 1981 | Smith, Jr. | 525/88.
|
| 4311628 | Jan., 1982 | Abdou-Sabet et al. | 525/232.
|
| 4361686 | Nov., 1982 | Zarr et al. | 526/143.
|
| 4375531 | Mar., 1983 | Ross | 525/93.
|
| 4429079 | Jan., 1984 | Shibata et al. | 525/240.
|
| 4495334 | Jan., 1985 | Matsuura et al. | 525/240.
|
| 4499241 | Feb., 1985 | Yoshimura et al. | 525/211.
|
| 4540753 | Sep., 1985 | Cozewith et al. | 526/88.
|
| 4716207 | Dec., 1987 | Cozewith et al. | 526/169.
|
| 4786697 | Nov., 1988 | Cozewith et al. | 526/88.
|
| 4789714 | Dec., 1988 | Cozewith et al. | 526/88.
|
| 4792595 | Dec., 1988 | Cozewith et al. | 526/348.
|
| 4843129 | Jun., 1989 | Spenadel et al. | 525/240.
|
| 4874820 | Oct., 1989 | Cozewith et al. | 525/53.
|
| 4882406 | Nov., 1989 | Cozewith et al. | 526/336.
|
| 5011891 | Apr., 1991 | Spenade et al. | 525/211.
|
| Foreign Patent Documents |
| 67138 | Dec., 1987 | EP.
| |
| 59-159842 | Oct., 1984 | JP.
| |
| 61-16943 | Jan., 1986 | JP.
| |
| 1160791 | Aug., 1969 | GB.
| |
Other References
Abstract of JP60072948-Japan Syn. Rubber-Apr. 1985.
Ferdinand C. Stehling, Terry Huff, C. Stanely Speed, and G. Wissler,
Journal of Applied Polymer Science, vol. 26, "Structure and Properties of
Rubber-Modified Polypropylene Impact Blends," John Wiley & Sons, Inc.
(1981), pp. 2693-2711.
Natta et al., "Polyolefin Elastomers" pp. 1583-1668.
Shih et al., "The Effect of Molecular Weight and Molecular Weight
Distribution on the Non-Newtonian Behavior of Ethylene Propylene Diene
Polymers" Tables II and III.
|
Primary Examiner: Seccuro, Jr.; Carman J.
Attorney, Agent or Firm: Skinner; William A.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a division of U.S. application Ser. No. 07/321,367,
filed Mar. 9, 1989 now abandoned, which is a division of U.S. application
Ser. No. 07/835,211, filed Mar. 3, 1986 now issued as U.S. Pat. No.
4,843,129.
Claims
What is claimed is:
1. A composition comprising:
(a) at least one elastomer copolymer comprising ethylene and at least one
other alpha olefin, having a weight average molecular weight of at least
20,000, and at least one of M.sub.w /M.sub.n less than 2 and M.sub.z
/M.sub.w less than 1.8, wherein at least two portions of essentially each
copolymer chain of said copolymer, each portion comprising at least 5 wt.%
of the chain, differ in composition from one another by at least about 5
wt.% ethylene;
(b) at least one plastic composition; and
(c) at least one copolymer, in an amount equal to approximately 80 wt.% or
less of the composition, comprising a plurality of Ziegler-Natta catalyzed
ethylene alpha olefin polymer chains, substantially each of said chains
being end capped with at least one functional group-containing unit which
is otherwise essentially absent from said copolymer chains, said
functional group being incorporated as a polymer unit selected from the
group consisting of:
##STR7##
the monomers thereof, and the mixtures thereof; wherein R.sub.1 through
R.sub.4 are hydrocarbons with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated, branched or unbranched, aliphatic,
aromatic, cyclic, or polycyclic hydrocarbons, wherein R.sub.5 is the same
as R.sub.4 but may additionally be hydrogen; and wherein x=1-10,000.
2. A composition comprising:
(a) at least one elastomer copolymer comprising ethylene and at least one
other alpha olefin, having a weight average molecular weight of at least
20,000, and at least one of M.sub.w /M.sub.n less than 2 and M.sub.z
/M.sub.w less than 1.8, wherein at least two portions of essentially each
copolymer chain of said copolymer, each portion comprising at least 5 wt.%
of the chain, differ in composition from one another by at least about 5
wt.% ethylene;
(b) at least one plastic composition; and
(c) at least one copolymer, in an amount equal to 80 wt.% or less of the
composition, comprising a plurality of copolymer chains, substantially
each of said chains being a Ziegler-Natta catalyzed ethylene alpha olefin
polymer chain end capped with at least one functional group-containing
unit which is otherwise essentially absent from said polymer chain.
3. The composition as defined by claim 2 wherein said functional group is
selected from the group consisting of: --CO.sub.2 H, --OH, --SH, --X,
--C--C--benzene, --C--C--(pyridine), --SO.sub.2 H, SO.sub.3 H, and
mixtures thereof, wherein X is a halide selected from the group consisting
of fluorine, chlorine, bromine, and iodine.
4. The composition as defined by claim 2 wherein said functional group is
selected from the group consisting of: isocyanates, urethanes, nitriles,
aromatic ethers and aromatic carbonates.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to novel blends of elastomers and plastic
compositions, and to novel processes for producing such blends.
More specifically, the plastics which may be employed in these blends
include polypropylenes, polyethylenes, including high density polyethenes,
low density polyethylenes, and linear low density polyethylenes,
polystyrenes, polyvinyl chlorides, polycarbonates, polyamides (nylons),
polyesters, polyphenylene oxides, ethylene/methylacrylate copolymers,
polybutylenes, polyvinyl acetates, ethylene/vinyl acetate copolymers,
polymethyl methacrylates, acrylonitrile-butadiene-styrenes, acetals,
alkyds, acrylics, polyethyl methacrylates, and heteroblock
propylene-ethylene copolymers. Also suitable are mixtures of two or more
of such plastic compositions, especially mixtures of polypropylene and
polyethylene, including high density polyethylene (HDPE), low density
polyethylene (LDPE), and linear low density polyethylene.
Among the suitable polypropylenes are those disclosed in SMITH, Jr. (U.S.
Pat. No. 4,059,651), HUFF (U.S. Pat. No. 4,087,485), FIELDING et al. (U.S.
Pat. No. 4,087,486), HUFF (U.S. Pat. No. 4,221,882), SMITH, Jr. (U.S. Pat.
No. 4,251,646), and ROSS (U.S. Pat. No. 4,375,531), the disclosures of
which are hereby incorporated by reference thereto.
Suitable elastomers for use in the blend are the compositions disclosed in
related U.S. Pat. Nos. 4,540,753 (hereinafter COZEWITH et al); 4,716,207;
4,874,820; 4,786,697; 4,789,714; and 4,882,406, all issued to Cozewith et
al.
2. Background Description of Relevant Materials
For convenience, certain terms that are repeated throughout the present
specification are defined below:
a) Inter-CD defines the compositional variation, in terms of ethylene
content, among polymer chains. It is expressed as the minimum deviation
(analogous to a standard deviation) in terms of weight percent ethylene
from the average ethylene composition for a given copolymer sample needed
to include a given weight percent of the total copolymer sample which is
obtained by excluding equal weight fractions from both ends of the
distribution. The deviation need not be symmetrical. When expressed as a
single number, for example 15% Inter-CD, it shall mean the larger of the
positive or negative deviations. For example, for a Gaussian compositional
distribution, 95.5% of the polymer is within 20 wt.% ethylene of the mean
if the standard deviation is 10%. The Inter-CD for 95.5% wt.% of the
polymer is 20 wt.% ethylene for such a sample.
b) Intra-CD is the compositional variation, in terms of ethylene, within a
copolymer chain. It is expressed as the minimum difference in weight (wt.)
% ethylene that exists between two portions of a single copolymer chain,
each portion comprising at least 5 weight % of the chain.
c) Molecular weight distribution (MWD) is given a measure of the range of
molecular weights within a given copolymer sample. It is characterized in
terms of at least one of the ratios of weight average to number average
molecular weight,M.sub.w /M.sub.n, and Z average to weight average
molecular weight, M.sub.z /M.sub.w, where
##EQU1##
Ni is the number of molecules of weight Mi.
Ethylene-propylene copolymers, particularly elastomers, are important
commercial products. Two basic types of ethylene-propylene copolymers are
commercially available. Ethylene-propylene copolymers (EPM) are saturated
compounds requiring vulcanization with free radical generators such as
organic peroxides. Ethylene-propylene terpolymers (EPDM) contain a small
amount of non-conjugated diolefin, such as dicyclopentadiene,
1,4-hexadiene, or ethylidene norbornene, which provides sufficient
unsaturation to permit vulcanization with sulfur. Such polymers that
include at least two monomers, i.e., EPM and EPDM, will hereinafter be
collectively referred to as copolymers.
These copolymers have outstanding resistance to weathering, good heat aging
properties and the ability to be compounded with large quantities of
fillers and plasticizers, resulting in low cost compounds which are
particularly useful in automotive and industrial mechanical goods
applications. Typical automotive uses are in tire sidewalls, inner tubes,
radiator and heater hose, vacuum tubing, weather stripping and sponge
doorseals, and as Viscosity Index (V.I.) improvers for lubricating oil
compositions. Typical mechanical goods uses are for appliance, industrial
and garden hoses, both molded and extruded sponge parts, gaskets and
seals, and conveyor belt covers. These copolymers also find use in
adhesives, appliance parts, as in hoses and gaskets, wire and cable, and
plastics blending.
The efficiency of peroxide curing depends on composition. As the ethylene
level increases, it can be shown that the "chemical" crosslinks per
peroxide molecule increase. Ethylene content also influences the
rheological and processing properties, because crystallinity, which acts
as physical crosslinks, can be introduced. The crystallinity present at
very high ethylene contents may hinder processibility, and may make the
cured product too "hard" at temperatures below the crystalline melting
point to be useful as a rubber.
As can be seen from the above, based on their respective properties, EPM
and EPDM find many, varied uses. It is known that the properties of such
copolymers which make them useful in a particular application are, in
turn, determined by their composition and structure. For example, the
ultimate properties of an EPM or EPDM copolymer are determined by such
factors as composition, compositional distribution, sequence distribution,
molecular weight, and molecular weight distribution (MWD).
It is well known that the breadth of the MWD can be characterized by the
ratios of various molecular weight averages. One of such averages is the
ratio of weight average to number average molecular weight (M.sub.w
/M.sub.n). Another of the ratios is the Z average molecular weight to
weight average molecular weight (M.sub.z /M.sub.w).
Copolymers of ethylene and at least one other alphaolefin monomer,
including EPM and EPDM polymers, which are intramolecularly heterogeneous
and intermolecularly homogenous, and which have a narrow MWD,
characterized as at least one of M.sub.w /M.sub.n less than 2 and M.sub.z
/M.sub.w less than 1.8, have improved properties in lubricating oil. Such
copolymers are disclosed in COZEWITH et al., which is incorporated herein
by reference. For convenience, such polymers are hereinafter referred to
as narrow MWD copolymers. Copolymers having MWD with both M.sub.w /M.sub.n
greater than or equal to 2 and M.sub.z /M.sub.w greater than or equal to
1.8 are hereinafter referred to as broad MWD copolymers.
It is generally recognized that the cure rate and physical properties of
copolymers of ethylene and at least one other alpha-olefin monomer are
improved as MWD is narrowed. Narrow MWD polymers have superior cure and
tensile strength characteristics over such polymers having broader MWD.
However, the advantages in physical properties gained from having a narrow
MWD are sometimes offset by the poorer processability of such materials.
They are often difficult to extrude, mill, or calendar. Nevertheless, is
certain instances the narrow MWD copolymer is advantageous in plastics
blending.
As to milling behavior of EPM or EPDM copolymers, this property varies
radically with MWD Narrow MWD copolymers crumble on a mill, whereas broad
MWD materials will band under conditions encountered in normal processing
equipment. Broader MWD copolymer has a substantially lower viscosity than
narrower MWD polymer of the same weight average molecular weight.
Thus, there exists a continuing need for discovering polymers with unique
properties and compositions. This is easily exemplified with reference to
the area of blends of elastomers and plastics having various utilities.
Plastic-elastomer blends comprising a discontinuous phase of the elastomer
dispersed within a continuous phase of the plastic find various uses, such
as in battery cases. For such blends, an intimate dispersion of the
elastomer discontinuous phase within the plastic composition continuous
phase is a desirable property.
Blends comprising cocontinuous phases of plastic and elastomer tend to have
greater impact strength than the pure plastic compositions, and are useful
in such products as automobile bumpers.
It is highly desirable in plastic-elastomer blends, particularly the
continuous-discontinuous phases blends, to attain a higher Gardner impact
strength without a corresponding lowering of knit line toughness or
stiffness.
U.S. Pat. No. 4,059,651 discloses a blend of 70-98 wt.% polypropylene, 2-30
wt.% EPDM elastomer, and halogenated phenol adehyde resin present in an
amount of about 1-20 parts per 100 parts of elastomer. The elastomer is
disclosed as containing about 40-80 wt.% ethylene and about 2-12 wt.%
diene with the balance being propylene. The components are mixed by
conventional techniques and heated at above the melting point of the
propylene, e.g., 300.degree.-400.degree. F. Alternatively, the halogenated
phenol aldehyde resin may first be mixed with the polypropylene at these
same temperatures, with the elastomer mixed in thereafter. After the
mixing and heating, the blend may be molded.
U.S. Pat. No. 4,087,485 to Huff discloses a blend comprising about 2-20% by
weight ethyelene-propylene copolymer elastomer, 70-90% by weight
polypropylene, and about 1-15% by weight LDPE. The elastomer may further
include a nonconjugated diene. The blend may be prepared by mixing with
conventional equipment at 350.degree.-400.degree. F. for about 4-7
minutes, with conventional agents employed for curing.
U.S. Pat. No. 4,088,714 to Huff discloses a blend comprising 40-90 wt.%
EPR, EPM, or EPDM copolymer, 14-20 wt.% cross-linkable low density
polyethyelene, and less than 50 wt.% isotactic polypropylene. Three
radical generating or crosslinking agents such organic peroxides are used
to cross-link the elastomer and the cross-linkable low density
polyethylene. Triallylcyanurate is employed to enhance the curing and
increase resiliency, tensile strength, and impact strength.
U.S. Pat. No. 4,221,882 to Huff discloses blends comprising 45-67%
polypropylene, 30-45% polyethylene, and 3.5-11% ethylene-propylene
copolymer. The polypropylene and ethylene-propylene compolymer are
premixed by conventional means and heated to about 204.degree. C. The
pre-blend is then pelletized or powdered and mixed with virgin high
density polyethylene, and melt-mixed as an extruder let down, normally at
about 204.degree. C. The final blend is then employed for molding parts.
U.S. Pat. No. 4,251,646 to Smith, Jr. discloses a blend of 60-90% by weight
polypropylene, 30-5% by weight thermoplastic crystalline heteroblock
propylene-ethylene copolymer, and 30-5% ethylene-propylene copolymer. The
blends are processed by conventional techniques at temperatures above
200.degree. C., are readily extrudable and moldable.
U.S. Pat. No. 4,375,531 to Ross discloses visbroken polymeric blends
comprising a first component selected from a group consisting of block
propylene-ethylene copolymers, reactormade intimate mixtures of
polypropylene and randomly oriented copolymers of proplyene and ethylene,
and blends of propylene and randomly oriented copolymers of propylene and
ethylene, and a second component selected from the group consisting of low
density polyethylene, ethylene-vinyl acetate copolymer, acrylate-modified
polyethylenes, high density polyethylenes, ethylene-propylene rubber (EPR
or EPDM), and blends thereof. The method for producing the composition
comprises first blending the components, and then visbreaking the
resulting blend. The visbreaking may be carried out in the presences of
peroxide concentrations of 50-2,000 ppm, and melt temperatures of
350.degree.-550.degree. F., in a single or twin screw extruder. Thermal
visbreaking, at temperatures in excess of 550.degree. F. and the absence
of free radial initiators and process or heat stabilizer additives, can
also be used.
"Structure and Properties of Rubber Modified Polypropylene Impact Blends,"
F. C. Stehling, T. Huff, C. S. Speed, and G. Wissler, Journal of Applied
Polymer Science, Vol. 26, pp. 2693-2711 (1981), discloses the dispersion
of poly(ethylene-co-propylene) (PEP) rubber and high density polyethylene
(HDPE) in polypropylene (PP) blends. Various PP-PEP blends, such as 90-10,
85-15, and 80-20 wt.% ratios, and PP-PEP-HDPE blends including 80-10-10,
85-7.5-7.5, and 90-5-5 wt.% ratios, were studied. In such ratios, PEP was
dispersed at a discontinuous phase within a continuous phase of PP in the
two component blends. In the three component blends, a discontinuous phase
of particles of PEP and HDPE was dispersed within a continuous phase of
PP; the particles of the discontinuous phase comprised an interior region
of HDPE surrounded by an outer layer of PEP.
None of these references discloses or suggests the use of the elastomer
compositions disclosed in the COZEWITH et al. patent or applications in
such plastic-elastomer blends.
SUMMARY OF THE INVENTION
It is, therefore, an object of the invention to provide and novel and
improved elastomer-plastic blends, utilizing the elastomer compositions
disclosed in the COZEWITH et al. patent and applications.
According to the invention, an elastomer-plastic composition is provided
which comprises:
(a) at least one copolymer having at least M.sub.w /M.sub.n less than 2 and
a M.sub.z /M.sub.w less than 1.8; and
(b) at least one plastic composition.
Preferably, the at least one copolymer has M.sub.w /M.sub.n less than 1.4,
and M.sub.z /M.sub.w less than 1.3.
The at least one copolymer may comprise ethylene and alpha-olefin monomer.
Preferably, the alpha-olefin monomer contains 3-18 carbon atoms. Most
preferably, it is propylene.
Ninety-five (95) wt.% of the copolymer chains of the copolymer may have an
ethylene composition that differs from its average weight percent ethylene
composition by not more than 15 wt.%, and at least two portions of
essentially each copolymer chain of the first copolymer, each portion
comprising at least 5 wt.% of the chain, may differ in composition from
one another by at least about 5 wt.% ethylene.
The copolymer may be an ethylene propylene terpolymer, which may comprise
ethylene, propylene, and a non-conjugated diene selected from the group
consisting of ethylidene norborene, 1,4-hexadiene, dicyclopentadiene,
vinyl norbornene, methylene norbornene, and mixtures thereof.
The plastic composition may be a thermoplastic composition, and may further
be selected from a group consisting of polypropylenes, polyethylenes,
ethylene/vinyl acetate copolymers, polyamides, polyphenyl oxides,
polycarbonates ethylene/methyl acrylate copolymers, polymethyl
methacrylates, polyvinyl chlorides, acrylonitrile-butadiene-styrenes,
polyethyl methacrylates, polystyrenes, polybutylenes, polyesters, acetals,
alkyds, polyvinyl acetates, acrylics, and heteroblock propyleneethylene
copolymers.
Preferably, the thermoplastic composition is polypropylene, or a
heteroblock propylene-ethylene copolymer.
Where the thermoplastic composition is polypropylene, it preferably
comprises approximately 98-50% by weight of the composition of the
invention, with the at least one copolymer comprising approximately 2-50%
by weight of the composition.
Where the thermoplastic composition is the heteroblock copolymer, this
copolymer preferably comprises approximately 98-50% by weight of the
composition. This heteroblock copolymer preferably comprises approximately
50-98% by weight propylene block and approximately 2-50% by weight post
block of ethylene and propylene. This post block preferably comprises
20-78% by weight ethylene.
The composition of the invention may include two or more plastics, such as
polyethylene and polypropylene.
In the composition in the invention, the one or more plastic compositions
may take the form of a continuous phase, and the one or more copolymers
may take the form of a discontinuous phase dispersed within this
continuous phase.
In such an embodiment, such continuous phase is preferably polypropylene
comprising at least 90 wt.% of the composition, and the discontinuous
phase is ethylenepropylene copolymer, ethylene-propylene terpolymer, or a
combination thereof, and comprises approximately 10 wt.% or less of the
composition.
The composition of the invention may further take the form of a continuous
phase comprising a first plastic composition, and a discontinuous phase,
dispersed within this continuous phase, comprising a second plastic
composition and at least one copolymer. In such an embodiment, the first
plastic composition is preferably polypropylene, and the second plastic
composition is preferably polyethylene; the copolymer is preferably an
ethylene-propylene copolymer, an ethylene-propylene terpolymer, or
mixtures thereof. Most preferably, the polypropylene comprises at least 85
wt.% of the composition, the polyethylene comprises approximately 5 wt.%
or less of the composition, and the indicated copolymer or copolymers
comprises approximately 10 wt.% or less of the composition.
The at least one copolymer of the composition of the invention may comprise
a plurality of copolymer chains, substantially each of which comprises a
first segment, being in the form of one contiguous or a plurality of
discontinuous segments, comprising a copolymer of ethylene and an
alpha-olefin; and a second segment comprising a copolymer of ethylene, an
alpha-olefin, and a coupling agent, said second segment constituting less
than 50% by weight of said copolymer chain and being in the form of one
contiguous segment or a plurality of discontinuous segments. The coupling
agent is cross-linkable under conditions which do not cross-link said
first segment to any substantial extent. Preferably, this copolymer has at
least one of M.sub.w /M.sub.n less than 2 and a M.sub.z /M.sub.w less than
1.8.
The indicated alpha-olefin may be propylene. The coupling agent may be a
Ziegler copolymerizable diene preferably selected from the group
consisting of norbornadiene, vinyl norbornene, and butenyl norbornene. In
the alternative, the coupling agent may be a cross-linkable diene
preferably selected from the group consisting of ENB, 1,4-hexadiene and
dicyclopentadiene.
The elastomer of the composition of the invention may comprise at least one
nodular ethylene-alpha-olefin copolymer product of copolymer chains
comprising a nodule region of substantial cross-linking of copolymer
chains second segments, with substantially uncrossed-linked copolymer
chain first segments extending therefrom. Preferably, the chain first
segments of the nodular copolymer are in the form of one contiguous
segment or a plurality of discontinuous segments, and comprise a copolymer
chain of ethylene and an alpha-olefin, while the chain second segments
comprise a copolymer of ethylene, alpha-olefin, and a coupling agent. Most
preferably, these second segments constitute less than 50% by weight of
each copolymer chain formed by the first and second segments, and are in
the form of one contiguous segment or a plurality of discontinuous
segments.
In this embodiment, the coupling agent may be a Ziegler copolymerizable
diene, preferably selected from the group consisting of norbornadiene,
vinyl norbornene, and butenyl norbornene. Alternatively, the coupling
agent may be a cross-linkable diene, preferably selected from a group
consisting of ENB, 1,4-hexadiene, and dicyclopentadiene.
The elastomer of the composition of the invention may comprise a copolymer
of ethylene and at least one other alpha-olefin monomer, which copolymer
is a superposition of two or more copolymers modes each having a MWD
characterized by at least one of M.sub.w /M.sub.n less than 2 and a
M.sub.z /M.sub.w less than 1.8. Preferably, the at least one other
alpha-olefin monomer contains 3-18 carbon atoms.
This copolymer may consist essentially ethylene, propylene, and straight
chain acyclic diene selected from the group consisting of 1,4-hexadiene
and 1,6-octadiene. Alternatively, this copolymer may consist essentially
of ethylene, propylene, and 5-ethylidene-2-norbornene.
The composition of the invention may comprise:
(a) an ethylene-alpha olefin copolymer;
(b) one or more plastic compositions; and
(c) at least one copolymer, in an amount equal to approximately 80 wt.% or
less of the composition, comprising a plurality of Ziegler-Natta catalyzed
polymer chains, substantially each of said chains being end capped with at
least one functional group-containing unit which is otherwise essentially
absent from said copolymer chains, said functional group being
incorporated in a polymer selected from the group consisting of:
##STR1##
the monomers thereof, and the mixtures thereof; wherein R.sub.1 through
R.sub.4 are hydrocarbons with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated, branched or unbranched, aliphatic,
aromatic, cyclic, or polycyclic hydrocarbons, wherein R.sub.5 is the same
as R.sub.4 but may additionally be hydrogen; and wherein x=1-10,000.
In the alternative the at least one copolymer present in an amount equal to
80 wt.% or less of the composition may comprise a plurality of copolymer
chains, substantially each of said chains being a Ziegler-natta catalyzed
polymer chain end capped with at least one functional group-containing
unit which is otherwise essentially absent from said polymer chain.
The indicated functional group may be selected from the group consisting
--CO.sub.2 H, --OH, --SH, --X, --C--C--benzene, --C--C--(pyridine),
--SO.sub.2 H, SO.sub.3 H, and mixtures thereof, wherein X is a halide
selected from the group consisting of fluorine, chlorine, bromine, and
iodine.
Alternatively this functional group may be selected from the group
consisting of isocyanates, urethanes, nitriles, aromatic ethers and
aromatic carbonates.
The indicated functional group containing unit may be selected from the
group of polymers consisting of copolymers of ethylene and vinyl acetate;
ethylene and acrylic acid esters; vinyl acetate and fumaric acid esters;
styrene and maleic acid esters; olefins and maleic acid esters;
homopolyacrylates; and epoxidized natural rubber.
The composition of the invention may further comprise:
(a) at least one copolymer which comprises a plurality of copolymer chains,
substantially each comprising:
I. a first segment, being in the form of one contiguous segment or a
plurality of discontinuous segments, comprising a copolymer of ethylene
and an alpha-olefin; and
II. a second segment comprising a copolymer of ethylene, an alpha-olefin,
and at least one halogen-containing monomer selected from the group
consisting of:
A. an olefinic chlorosilane of the formula
SiRR.sub.x 'Cl.sub.3-X
wherein:
i) x is in the range 0-2;
ii) R is a Ziegler copolymerizable olefin; and
iii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons;
B. an olefinic hydrocarbon halide of the formula
RR'X
wherein:
i) R is a Ziegler copolymerizable olefin; and
ii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons; and
iii) X is a halogen;
said second segment constituting less than 50 percent by weight of said
copolymer chain, said second segment being in the form of one contiguous
segment or a plurality of discontinuous segments;
said at least one halogen-containing monomer being cross-linkable under
conditions which do not cross-link said first segment to any substantial
extent; and
(b) at least one plastic composition.
Alternatively, the elastomer of the composition of the invention may
comprise:
(a) at least one copolymer consisting essentially of a plurality of
copolymer chains having at least one of M.sub.w /M.sub.n less than 2 and
M.sub.z /M.sub.w less than 1.8, said copolymer comprising ethylene, an
alpha-olefin, and at least one halogen-containing monomer selected from
the group consisting of:
I. an olefinic chlorosilane of the formula:
SiRR.sub.x 'Cl.sub.3-x
wherein;
i) x is in the range of 0-2;
ii) R is a Ziegler copolymerizable olefin; and
iii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbon; and
II. an olefinic hydrocarbon halide of the formula:
RR'X
wherein:
i) R is a Ziegler copolymerizable diene; and
ii) R' is a hydrocarbon with 1-30 -carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons; and
iii) X is a halogen.
This copolymer may further comprise a non-conjugated diene selected from
the group consisting of 5-ethylidene-2-norbornene, 1,4-hexadiene,
dicylopentadiene, and mixtures thereof.
Further, in the alternative, the elastomer of the invention may comprise at
least one nodular copolymer product of copolymer chains comprising:
A. a nodule region of substantial cross-linking of copolymer chain second
segments substantially cross-linked by at least one cross-linking agent,
substantially each of said second segments comprising a copolymer of
ethylene, an alpha-olefin, and at least one halogen-containing monomer
selected from the group consisting of:
(a) an olefinic chlorosilane of the formula
SiRR.sub.x 'Cl.sub.3-x
wherein:
i) x is in the range 0-2;
ii) R is a Ziegler copolymerizable olefin; and
iii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons; and
(b) an olefinic hydrocarbon halide of the formula RR'X wherein:
i) R is a Ziegler copolymerizable olefin;
ii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons;
iii) X is a halogen; and
B. substantially uncross-linked copolymer chain first segments extending
therefrom, substantially each of said first segments comprising a
copolymer of ethylene and an alpha-olefin;
said halogen-containing monomer being cross-linkable under conditions which
do not cross-link said first segments to any substantial extent.
Where the indicated halogen-containing monomer is an olefinic chlorosilane,
it may be selected from the group consisting of vinyl
dimethylchlorosilane, vinyl ethyl dichlorosilane,
1-hexenyl-6-dimethylchlorosilane, 1-hexenyl-6-trichlorosilane,
1-octenyl-8-trichlorosilane, phenyl allyldichlorosilane,
5-trichlorosilyl-2-norbornene, and 5-methyldichlorosilyl-2-norbornene.
Where the indicated halogen-containing monomer is an olefinic hydrocarbon
halide, it may be selected from the group consisting of
5-chloromethyl-2-norbornene and 2-parachloromethylphenyl-5-norbornene.
These copolymers may be linked to the plastic through the indicated
halogen-containing monomer. Where the halogen-containing monomer is an
olefinic chlorosilane, such a link will form where the plastic composition
is a polycarbonate, a polyamide, a polyester, a polyphenylene oxide, or an
acetal. Where the halogen-containing monomer is an olefinic hydrocarbon
halide, the link will form where the plastic composition is a polyamide.
The composition of the invention may also be subjected to curing.
The invention is also directed to the process for preparing the previously
indicated compositions.
In one embodiment of the process, where the elastomer comprises a copolymer
having at least one of M.sub.w /M.sub.n less than 2 and M.sub.z /M.sub.w
less than 1.8, this elastomer is formed from a reaction mixture comprised
of catalyst, ethylene, and at least one other alpha-olefin monomer,
comprising conducting the polymerization of said at least one copolymer:
(a) in at least one mix-free reactor;
(b) with essentially one active catalyst species;
(c) using at least one reaction mixture which is essentially transfer-agent
free;
(d) in such a manner and under conditions sufficient to initiate
propagation of essentially all of said copolymer chains simultaneously,
wherein chains of said at least one copolymer are dispersed within the
reaction mixture.
This resulting elastomer is then blended with one or more plastics to form
the composition of the invention.
In preparing the composition of the invention wherein the elastomer
comprises a polymodal MWD copolymer, this copolymer may be prepared by
varying the previously indicated reaction process by any one of several
ways.
In one of these variations, reaction mixture is withdrawn from the reactor
at at least two predetermined times after initiation of the polymerization
and the copolymer withdrawn at each of said times is blended to form the
polymodal MWD copolymer. Another variation employs at least two catalyst,
each of which initiates the growth of polymer chains that obtain a
different average molecular weight than that initiated by the other
catalyst.
In a third alternative, at least two different mix-free reactors are
employed to form the different modes which are then blended to produce the
polymodal MWD copolymer.
In a fourth embodiment, the polymodal MWD copolymer is produced by adding a
catalyst reactivator to the reaction mixture after polymerization has
progressed for a finite period of time.
A fifth embodiment employs a catalyst system which generates multiple
active catalyst species, each initiating the growth of polymer chains that
obtain a different average molecular weight than those produced by other
catalyst species.
To prepare a composition of the invention wherein the elastomer is a
nodular compolymer, the previously indicated reaction process is varied by
permitting the polymerization to continue to at least 50% completion, at
which point a coupling agent is introduced into the reaction mixture. The
reaction is thereafter permitted to continue, thereby incorporating the
coupling agent into the polymer so as to form a nodular copolymer wherein
the polymer chains are linked to the coupling agent. The product which
results is blended with one or more plastics to produce the composition of
the invention.
To prepare an elastomer for the composition of the blend comprising
ethylene, one or more alpha-olefin monomers, and at least one halogen
containing monomer selected from the group consisting of
(a) olefinic chlorosilane of the formula
SiRR.sub.x 'Cl.sub.3-x
wherein;
i) x is in the range 0-2;
ii) R is a Ziegler compolymerizable olefin; and
iii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic aromatic cyclic, and polycyclic hydrocarbons; and
(b) olefinic hydrocarbon halide of the formula RR'X wherein;
i) R is a Ziegler copolymerizable olefin; and
ii) R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or unsaturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons; and
iii) X is a halogen;
wherein ethylene, one or more alpha-olefin monomers, and at least one of
the previously indicated halogen-containing monomers are introduced into
the previously described reaction process. The resulting copolymer is
blended with one or more plastic compositions to produce the composition
of the present invention.
A narrow-broad ethylene alpha-olefin copolymer, i.e., an ethylene
alpha-olefin copolymer composition comprising:
(i) a first copolymer having at least one of M.sub.w /M.sub.n less than 2
and M.sub.z /M.sub.w less than 1.8; and
(ii) a second copolymer having both M.sub.w /M.sub.n greater than or equal
to 2 and M.sub.z /M.sub.w greater than or equal to 1.8; may be prepared
for incorporation into the composition of the invention by forming the
first polymer by the previously described process, reacting a second
reaction mixture to produce the second copolymer, and then blending the
first and second copolymers to form the elastomer for use with the
composition of the invention. Subsequently, this elastomer is blended with
one or more plastic compositions to form the composition of the invention.
Any of these indicated processes may further be subjected to a curing step
for curing the composition.
The blends of the invention can have utility in high impact applications.
They can be employed in films, laminates, fabric coatings, tapes, and
molded and extruded products, including sheet extrusion products.
The preferred elastomers for use in the blends of the invention are the
single mode narrow MWD EPM and EPDM copolymers. The preferred plastic
compositions are polypropylene, polyethylene, particularly high density
polyethylene, polystyrene, ethylene/vinyl acetate copolymer,
ethylene/methyl methacrylate copolymer, and heteroblock propylene-ethylene
copolymers. The use of polypropylene and polyethylene together is also
preferred.
Where the plastic composition of the invention is polypropylene, the blends
preferably comprise approximately 2-50 weight percent elastomer and
approximately 98-50 weight percent polypropylene.
Blends employing heteroblock propylene-ethylene copolymer preferably
comprise approximately 2-50 weight percent of elastomer and approximately
98-50 weight percent of the heteroblock copolymer. The heteroblock
copolymer preferably comprises approximately 50-98 weight percent, more
preferably approximately 60-95 weight percent, of a polypropylene block,
and preferably approximately 2-50 weight percent, more preferably
approximately 5-40 weight percent of a post block of ethylene and
propylene. The post block preferably comprises approximately 20-75 weight
percent, more preferably 25-50 weight percent ethylene.
DETAILED DESCRIPTION OF THE INVENTION
The preferred COZEWITH et al. composition for use with the blends of this
invention are the single mode narrow MWD copolymers, in particular the EPM
and EPDM copolymers, as disclosed in U.S. Pat. No. 4,540,753.
These narrow MWD copolymers in accordance with the present invention are
preferably made in a tubular or batch reactor operating under carefully
controlled conditions.
As indicated in COZEWITH et al. at column 7, lines 4-36, when a tubular
reactor is employed with monomer feed only at the tube inlet, ethylene
will be preferentially polymerized. The result is copolymer chains with
progressively lower ethylene and higher propylene concentration, as
schematically presented below:
##STR2##
This resulting chain is intramolecularly heterogenous.
As indicated at column 7, lines 37-48, where more than two monomers are
used in the production of the narrow and broader MWD copolymers, as in the
production of EPDM, all properties related to homogeneity and
heterogeneity will refer to the relative ratio of ethylene to the other
monomers in the chain. Further, as earlier indicated, the property related
to intramolecular compositional dispersity shall be referred to as
Intra-CD, and the property related to intermolecular compositional
dispersity shall be referred to as Inter-CD.
The preferred copolymers for the narrow MWD copolymers are comprised of
ethylene and at least one other alphaolefin. It is believed that such
alpha-olefins may include those containing 3 to 18 carbon atoms, e.g.,
propylene, butene-1, pentene-1, etc. Alpha-olefins of 3 to 6 carbons are
preferred due to economic considerations. The most preferred copolymers
for the narrow MWD copolymers are those comprised of ethylene and
propylene, or of ethylene, propylene and diene.
As is well known to those skilled in the art, copolymers of ethylene and
higher alpha-olefins such as propylene often include other polymerizable
monomers. Typical of these other monomers may be non-conjugated dienes
such as the following non-limiting examples:
a. straight chain acyclic dienes such as: 1,4-hexadiene; 1,6-octadiene;
b. branched chain acyclic dienes such as: 5-methyl-1,4-hexadiene;
3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and the mixed
isomers of dihydromyrcene and dihydroocimene;
c. single ring alicyclic dienes such as: 1,4-cyclohexadiene;
1,5-cyclooctadiene; and 1,5cyclododecadiene;
d. multi-ring alicyclic fused and bridged ring dienes such as:
tetrahydroindene; methyltetrahydroindene; dicyclopentadiene;
bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and
cycloalkylidene norbornenes such as 5-methylene-2-norbornene (NMB),
5-ethylidene-2-norbornene (ENB), 5-(4-cyclopentenyl)-2-norbornene;
5-cyclohexylidene-2-norbornene.
Of the non-conjugated dienes typically used to prepare these copolymers,
dienes containing at least one of the double bonds in a strained ring are
preferred. The most preferred diene is 5-ethylidene-2-norbornene (ENB).
The amount of diene (wt. basis) in the copolymer could be from about 0% to
20%, with 0% to 15% being preferred. The most preferred range is 0% to
10%.
As already noted, the most preferred copolymer for the narrow MWD copolymer
is ethylene-propylene or ethylene-propylene-diene. In either event, the
average ethylene content of the copolymer could be as low as about 10% on
a weight basis. The preferred minimum is about 25%. A more preferred
minimum is about 30%. The maximum ethylene content could be about 90% on a
weight basis. The preferred maximum is about 85%, with the most preferred
being about 80%.
The molecular weight of the narrow MWD copolymer can vary over a wide
range. It is believed that the weight average molecular weight could be as
low as about 2,000. The preferred minimum is about 10,000. The most
preferred minimum is about 20,000. It is believed that the maximum weight
average molecular weight could be as high as about 12,000,000. The
preferred maximum is about 1,000,000. The most preferred maximum is about
750,000.
The molecular weight distribution (MWD) of the narrow MWD copolymer is very
narrow, as characterized by at least one of a ratio of M.sub.w /M.sub.n of
less than 2 and a ratio of M.sub.z /M.sub.w of less than 1.8. As relates
to EPM and EPDM, some typical advantages of such copolymers having narrow
MWD are greater resistance to shear degradation, and when compounded and
vulcanized, faster cure and better physical properties than broader MWD
materials.
The narrow MWD copolymer is produced by polymerization of a reaction
mixture comprised of catalyst, ethylene and at least one additional
alpha-olefin monomer. Solution polymerizations are preferred.
Any known solvent for the reaction mixture that is effective for the
purpose can be used in conducting such solution polymerizations. For
example, suitable solvents are hydrocarbon solvents such as aliphatic,
cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions
of such solvents. The preferred solvents are C.sub.12 or lower, straight
chain or branched chain, saturated hydrocarbons, C.sub.5 to C.sub.9
saturated alicyclic or aromatic hydrocarbons or C.sub.2 to C.sub.6
halogenated hydrocarbons. Most preferred are C.sub.12 or lower, straight
chain or branched chain hydrocarbons, particularly hexane. Nonlimiting
illustrative examples of solvents are butane, pentane, hexane, heptane,
cyclopentane, cyclohexane, cycloheptane, methyl cyclopentane, emthyl
cyclohexane, isooctane, benzene, toluene, xylene, chloroform,
chlorobenzenes, tetrachloroethylene, di-chloroethane and trichloroethane.
The composition of the narrow MWD copolymers can vary between chains as
well as along the length of the chain. It is preferable to minimize the
amount of interchain variation, which, as indicated, is measured by
Inter-CD. Inter-CD is characterized by the fraction and total composition
differences as more fully explained at column 7, lines 49-64 of COZEWITH
et al., and is measured by techniques using solvent compositions, as also
more fully described in this portion of the patent.
It is preferred that the Inter-CD of the copolymer is such that 95 wt.% of
the copolymer chains have an ethylene composition that differs from the
copolymer average weight percent ethylene composition by 15 wt.% or less.
The preferred Inter-CD is about 13% or less, with the most preferred being
about 10% or less.
It is also preferred that the Intra-CD of the narrow MWD copolymer be such
that at least two portions of an individual intramolecularly heterogeneous
chain, each portion comprising at least 5 weight percent of the chain,
differ in composition from one another by at least 5 weight percent
ethylene. The Intra-CD can be such that at least two portions of copolymer
chain differ by at least 10 weight percent ethylene. Differences of at
least 20 weight percent, as well as of at least 40 weight percent
ethylene, are also considered to be in accordance with the present
invention. Having a polymer chain which is rich in propylene at one end
and rich in ethylene at the other end is advantageous for morphology and
property control in blends of polyethylene and polypropylene plastics with
EDM and EPDM copolymers.
Intra-CD for the narrow MWD copolymer is established by an experimental
procedure wherein Inter-CD is first established as previously discussed,
and the polymer chain is then broken into fragments alongs its contour,
whereupon the Inter-CD of the fragments is determined. The difference in
the two results is due to Intra-CD, as more fully represented at the
illustrative example at column 8, line 33 through column 9, line 31 of
COZEWITH et al.
In order to determine the fraction of a polymer which is intramolecularly
heterogenous in a mixture of polymers combined from several sources, the
mixture must be separated into fractions which show no further
heterogeneity upon subsequent fractionation. These fractions are
subsequently fractured and fractionated to reveal which are heterogeneous.
The properties of the required fragments, and the necessary fractionation
technique, are described in detail at column 9, line 39 through column 10,
line 38 of COZEWITH et al.
Ethylene content for the narrow MWD copolymer can be measured by ASTM
tests, and proton and carbon 13 nuclear magnetic resonance, as more fully
described at column 10, lines 39-54 of COZEWITH et al.
Molecular weight and molecular weight distributions can be measured by
chromatography techniques, and numerical analyses are performed by
computer, as more fully described at column 10, line 55 through column 11,
line 8 of COZEWITH et al.
The polymerization process for producing a single mode narrow MWD copolymer
should be conducted such that:
a. the catalyst system produces essentiallly one active catalyst species;
b. the reaction mixture is essentially free of chain transfer agents; and
c. the polymer chains are essentially all initiated simultaneously, which
is at the same time for a batch reactor, or at the same point along the
length of the tube for a tubular reactor.
The narrow MWD copolymer may be produced in a mix-free reactor system,
which is one in which substantially no mixing occurs between portions of
the reaction mixture that contain polymer chains initiated at different
times. A suitable process, as disclosed in COZEWITH et al., employs a
tubular reactor with a catalyst system that gives essentially one active
catalyst species, selecting polymerization conditions such that all the
polymer chains are initiated at the reactor inlet, and chain transfer is
substantially absent along the tube length.
As disclosed in COZEWITH et al., a single continuous flow stirred tank
reactor (CFSTR) will mix polymer chains initiated at different times, and
is therefore not suitable for producing the narrow MWD copolymer. However,
it is well known that 3 or more stirred tanks in series with all of the
catalyst fed to the first reactor can approximate thee performance of a
tubular reactor. Accordingly, such tanks in series are considered to be in
accordance with the present invention, and fall within the term "tubular"
as used herein.
Another suitable reactor is a batch reactor, preferably equipped with
adequate agitation, to which the catalyst, solvent, and monomer are added
at the start of the polymerization. The charge of reactants is then left
to polymerize for a time long enough to produce the desired product. For
economic reasons, a tubular reactor is preferred to a batch reactor for
performing the processes of this invention.
The temperature of the narrow MWD reaction mixture should also be kept
within certain limits. The temperature at the ractor inlet should be high
enough to provide complete, rapid chain initiation at the start of the
polymerization reaction. The length of time the reaction mixture spends at
high temperature must be short enough to minimize the amount of
undesirable chain transfer and catalyst deactivation reactions.
Temperature control of the narrow MWD reaction mixture, as described more
fully in COZEWITH et al., is maintained by using prechilled feed and
operating the reactor adiabatically. As an alternative to feed prechill, a
heat exchanger, as more fully described in COZEWITH et al., may be
employed. Well known autorefrigeration techniques may be used in the case
of batch reactors or multiple stirred reactors in series.
If adiabatic reactor operation is used, the inlet temperature of the
reactor feed could be about from -50.degree. C. to 150.degree. C. It is
believed that the outlet temperature of the reaction mixture could be as
high as about 200.degree. C. The preferred maximum outlet temperature is
about 70.degree. C. The most preferred maximum is about 50.degree. C.
Certain reaction parameters for the process of producing the narrow MWD
copolymer, such as preferred maximum copolymer concentration at the
reactor outlet, flow rate of the reaction mixture, and residence time of
the reaction mixture in the mix-free reactor for the process of making the
narrow MWD copolymer, are more fully described at column 17, line 57
through column 18, line 23 of COZEWITH et al.
Briefly as to these parameters, the most preferred maximum polymer
concentration at the reactor outlet is 15wt/100 wt diluent, with a
preferred minimum of 2wt/100wt diluent, and a most preferred minimum of at
least 3wt/100wt diluent. As to residence time, a preferred minimum is
about 10 seconds, and a most preferred minimum is about 15 seconds; the
maximum could be as high as about 3,600 seconds, with a preferred maximum
of about 1,800 seconds, and a most preferred maximum of about 900 seconds.
The flow rate should be high enough to provide good mixing of the
reactants in the radial direction and minimize mixing in the axial
direction.
Additional solvents and reactants may be added along the length of a
tubular reactor, or during the course of polymerization in a batch
reactor.
In the process for making the narrow MWD copolymer, it is essential that
the polymer chains are all initiated simultaneously.
In addition to the disclosed reactor systems, others having the benefit of
the present disclosure may be employed. Further, more than one reactor
could be used in parallel, or in series with a multiple monomer feed.
Accordingly, processes for producing a single mode narrow MWD copolymer in
accordance with the present invention are carried out:
(a) in at least one mix-free reactor,
(b) using a catalyst system that produces essentially one active catalyst
species,
(c) using at least one reaction mixture which is essentially transfer
agent-free, and
(d) in such a manner and under conditions sufficient to initiate
propagation of essentially all polymer chains simultaneously.
Any of the process means disclosed in the COZEWITH et al. patent, using the
reaction components, parameters, additives, and apparatus also disclosed
therein, may be employed to produce the narrow MWD copolymer. The M.sub.w
/M.sub.n value of this copolymer will be less than 2.0, and as low as
1.2-1.5.
As more fully described at column 13, line 64 through column 14, line 25,
of COZEWITH et al., the catalyst used in the process for producing the
narrow MWD copolymer should preferably be such as to yield essentially one
active catalyst species in the reaction mixture. As also more fully
discussed at this portion of COZEWITH et al., additional active catalyst
species can be present which produce as much as 35% by weight of the total
copolymer, but preferably less than 10% or less by weight of the
copolymer, if only the narrow MWD polymer is to be formed. Accordingly,
where only the narrow MWD polymer is to be formed, the one active species
should provide for at least 65%, or preferably at least 90%, of the total
copolymer produced.
Techniques for measuring the activity of and for characterizing catalyst
species are discussed at column 14, lines 14-25 of COZEWITH et al.
The catalyst systems employed in producing the narrow MWD copolymer may be
those disclosed in COZEWITH et al., prepared as disclosed in this patent.
Catalyst system to be used in carrying out processes for producing the
narrow MWD copolymer may be Ziegler catalysts, which may typically
include:
(a) a compound of a transition metal, i.e., a metal of Groups I-B, III-B,
IV-B, VI-B, VII-B, and VIII of the Periodic Table, and
(b) an organometal compound of a metal of Groups I-A, II-A, II-B and III-A
of the Periodic Table.
The preferred catalyst system in practicing processes in accordance with
the present invention comprises a hydrocarbon soluble vanadium compound,
in which the vanadium valence is 3 to 5, an organo-aluminum compound, with
the proviso that the catalyst system yields essentially one active
catalyst species as described above. At least one of the vanadium
compound/organo-aluminum pair selected must also contain a valence-bonded
halogen.
In terms of formulas, vanadium compounds useful in practicing processes in
accordance with the present invention could be:
##STR3##
where X=0-3 and R=a hydrocarbon radical;
VCl.sub.4 ;
VO(AcAc).sub.2,
where AcAc=acetyl acetonate;
V(AcAc).sub.3 ;
VOCl.sub.x (AcAc).sub.3-x, (2)
where x=1 or 2;
VCl.sub.3.nB, and mixtures thereof
where n=2-3 and B=Lewis base capable of making hydrocarbon-soluble
complexes with VCl.sub.3, such as tetrahydrofuran,2-methyl-tetrahydrofuran
and dimethyl pyridine.
In formula (1) above, R preferably represents a C.sub.1 to C.sub.10
aliphatic, alicyclic or aromatic hydrocarbon radical such as ethyl (Et),
phenyl, isopropyl, butyl, propyl, n-butyl, i-butyl, hexyl, cyclohexyl,
octyl, naphtyl, etc. Non-limiting, illustrative examples of formula (1)
compounds are vanadyl trihalides, alkoxy halides and alkoxides such as
VOCl.sub.3 VOCl.sub.2 (OBu) where Bu=butyl, and VO(OC.sub.2
H.sub.5).sub.3. The most preferred vanadium compounds are VCl.sub.4,
VOCl.sub.3, and VOC.sub.2 (OR).
As already noted, the co-catalyst is preferably an organo-aluminum
compound. In terms of chemical formulas, these compounds could be as
follows:
______________________________________
AlR.sub.3, Al(OR')R.sub.2
AlR.sub.2 Cl, R.sub.2 Al--O--AlR.sub.2
AlR'RCl AlR.sub.2 I
Al.sub.2 R.sub.3 Cl.sub.3,
AlRCl.sub.2, and mixtures thereof
______________________________________
where R and R' represent hydrocarbon radicals, the same or different, as
described above with respect to the vanadium compound formula.
A preferred organo-aluminum compound is Al.sub.2 R.sub.3 Cl.sub.3.
The most preferred organo-aluminum co-catalyst is ethyl aluminum
sesquichloride (EASC)-Al.sub.2 Et.sub.3 Cl.sub.3.
Where the catalyst system used in producing the narrow MWD copolymer
comprises VCl.sub.4 and Al.sub.2 R.sub.3 Cl.sub.3, preferably where R is
ethyl, the mole ratio of aluminum/vanadium, as more fully described as
column 15, lines 37-54 of COZEWITH et al., should be at least 2, with a
preferred minimum of about 4, and a maximum of about 25, a preferred
maximum of about 17, and a most preferred maximum of about 15.
The catalyst system can be selected, and the reactor temperature set, so
that negligible chain transfer with aluminum alkyl or propylene occurs
along the reactor length. Essentially all chain growth must start near the
catalyst feed point. These requirements can be met with catalyst systems
containing EASC.
The catalyst components are preferably premixed, as is described in
COZEWITH et al. in more detail, and aged prior to introduction in to the
reactor. The preferred minimum aging period is about 0.1 second. More
preferably, this period is about 0.5 seconds; most preferably, about 1
second. The maximum aging period is about 200 seconds, or, more
preferably, about 100 seconds. Most preferably, this period is about 50
seconds.
The premixing can be performed at temperatures of 40.degree. C. or below.
More preferably, premixing is performed at 25.degree. C. or below; most
preferably, at 15.degree. C. or below.
The elastomer composition comprising a narrow MWD copolymer and a broad MWD
copolymer, is also suitable for use in the blends of the invention.
The narrow MWD component of this composition is the narrow MWD copolymer
previously described, prepared by the indicated processes.
No restrictions apply to processes for producing the broader MWD copolymer
which are well known. This process can be practiced with a variety of
catalyst systems and polymerization conditions, provided that the desired
quantity and molecular weight of polymer is obtained. The same monomers,
solvents, and catalysts as disclosed for producing the narrow MWD
copolymer may be used to produce the broader MWD copolymer. Reaction
parameters may be varied to produce the broader MWD of this copolymer.
Such reaction parameters which may be varied are temperature at the inlet
and/or outlet of the reactor, as well as through the body of the reactor.
Chain transfer agents such as hydrogen or diethyl zinc, as disclosed in
COZEWITH et al., may be added to the process to broaden MWD.
MWD may further be broadened by catalyst deactivation, as disclosed in
COZEWITH et al.
MWD may further be broadened by adding diethyl aluminum chloride (DEAC) to
the reaction.
The broader MWD copolymer may be prepared in a tubular reactor or in a
stirred tank. The stirred tank may be a continuous flow stirred tank
reactor (CFSTR).
According to one novel process for producing the narrow-broad MWD
composition, a first reactor or reactors operating at conditions chosen to
produce the narrow MWD copolymer can be operated in series or in parallel
with a second reactor operating to produce the broader MWD copolymer. The
second tubular reactor can be separate from the first reactor, or it can
be an extension thereof, as long as the correct polymerization conditions
are imposed.
When the second reactor is a continuous flow stirred reactor, typical
operating conditions are a temperature of 20.degree.-70.degree. C. and a
residence time of 5-60 minutes. The exit polymer concentration from this
reactor is preferably in the range of 2 wt/100 wt diluent to 20 wt/100 wt
diluent. Any of the catalyst systems previously disclosed can be used in
the second reactor to form the second polymer. It is well known in the art
that the choice of catalyst components used in a continuous flow stirred
reactor influences the MWD of the polymer produced. By proper selection of
the catalyst a second polymer with M.sub.w /M.sub.n between 2 and 100 can
be obtained.
The narrow-broad MWD composition can be formed by first preparing the
narrow MWD copolymer in a mix free tubular reactor. This process utilizes
conditions sufficient to simultaneously initiate propagation of all
copolymer chains of the narrow MWD copolymer, and the reaction mixture
employed comprises a catalyst for generating essentially one catalyst
species having a life longer than the residence time in the reactor. Then,
this narrow MWD copolymer is reacted in a stirred tank reactor with
additional monomer to form the broader MWD copolymer.
The composition can also be produced by preparing the broader MWD copolymer
in a second tubular reactor operated in parallel with the tubular reactor
used to prepare the narrow MWD copolymer, and then blending the products.
The composition can be prepared in the tubular reactor used to prepare the
narrow MWD copolymer. The broader MWD copolymer of the blend can be formed
by injecting a catalyst, or a transfer agent, or additional reaction
mixture, at at least one location along the tubular reactor.
Where the narrow MWD copolymer comprises ethylene-propylene-coupling agent
containing chains, the broader MWD copolymer components can be prepared by
cross-linking the coupling agents to nodularize a portion of the chains,
and the nodular chains are then blended with the narrow MWD chains.
Another means comprises first preparing the broader MWD copolymer in a
tubular reactor by means of a catalyst suitable for preparing this
copolymer, and then injecting a catalyst suitable for preparing the narrow
MWD copolymer, and, alternatively, also injecting additional monomer, to
initiate the reaction for forming the narrow MWD copolymer.
In the case where broad and narrow components are generated
"simultaneously", the reactor is mix-free only for the narrow MWD catalyst
component. Initiation of the broad MWD component would extend over a
period of time which is comparable to chain lifetime, and may overlap at
some point with initiation of the narrow MWD copolymer. Substantially no
mixing occurs between portions of the reaction mixture that contain
polymer chains initiated by the narrow MWD catalyst at different times.
In the mix-free tubular reactor employed to prepare the narrow MWD
copolymer, the broader MWE copolymer can be prepared by recycling a
portion of the narrow MWD copolymer from the reactor outlet to a point
along the reactor.
Another means for preparing the narrow-broad composition in a single
mix-free tubular reactor is by adding, during the process for preparing
the narrow copolymer, catalyst reactivator, and, optionally, additional
monomers, downstream of the reactor inlet to form the broader MWD
copolymer component.
The narrow MWD copolymer can be prepared in a mix-free batch reactor,
utilizing conditions sufficient to simultaneously initiate propagation of
all copolymer chains of the narrow MWD copolymer. The reaction mixture
employed comprises a catalyst for preparing essentially one catalyst
species, and is essentially free of transfer agents.
The narrow-broad MWD composition can also be formed by employing a batch
reactor, and then adding the resulting narrow MWD copolymer to the broad
MWD copolymer. It can also be formed by preparing the broader MWD
copolymer in a batch reactor, and thereafter blending it with the first
copolymer made in the batch reactor.
The narrow and broad MWD copolymers can be simultaneously formed in a
single batch reactor by introducing into the reaction mixture both
catalyst for generating essentially one catalyst species, to produce the
narrow MWD copolymer, and by also introducing a catalyst suitable for
forming the second copolymer.
The copolymers disclosed in the previously indicated Application No. U.S.
Pat. No. 4,789,714, comprising a superposition of two or more narrow MWD
copolymers, and hereinafter referred to, for convenience, as polymodal
copolymers, are also suitable for use with the blends of this invention.
As previously indicated, single mode MWD copolymers are produced by
carrying out a polymerization reaction:
(a) in at least one mix free reactor,
(b) using catalyst systems such that each component or mode in a MWD is
produced by essentially one active catalyst species,
(c) using at least one reaction mixture which is essentially transfer
agent-free, and
(d) in such a manner and under conditions sufficient to initiate
propagation of essentially all polymer chains made with a particular
catalyst species simultaneously.
To produce the polymodal MWD copolymer, these polymerization conditions are
used to generate each of the narrow MWD modes that comprise the final
polymer product. A number of techniques are available for achieving this:
1) In a single mix free reactor operated as described above, portions of
the polymer product can be withdrawn after varying times in a batch
reactor or at varying distances along a tubular reactor representing
different average molecular weights and these portions can be blended.
2) Mix-free reactors can be operated either in parallel or sequentially and
the products blended.
3) Two or more catalysts that form narrow MWD polymer of differing
molecular weight can be added at the onset of polymerization in a mix-free
reactor. Each catalyst must meet the requirements of minimizing chain
transfer and initiating simultaneous propagation of all the chains
produced by that catalyst.
4) A catalyst system that generates multiple active catalyst species can be
added at the start of the polymerization. Each catalyst species produced
must give simultaneous chain initiation and minimize chain transfer.
5) Additional catalyst and monomer, if desired, can be added at varying
lengths along a tubular reactor, or times in a batch reactor, to initiate
the formation of additional MWD modes. The catalysts can be the same or
different, as long as chains are initiated simultaneously and chain
transfer is minimized.
6) For catalyst systems that show a decay in activity as a function of time
due to deactivation, catalyst reactivator can be added during the course
of the polymerization to regenerate the dead catalyst and form a new mode
of narrow MWD copolymer.
Catalyst reactivators are well known in the art for increasing the
productivity of vanadium Ziegler catalysts. These materials rejuvenate
catalyst sites that have become inert due to termination reactions, and
thereby cause reinitiation of polymer chain growth. When added to a
reactor operating according to the process of this invention, catalyst
reactivators have an effect similar to that of adding a second catalyst
feed. Many reactivators are known, and examples of suitable materials can
be found in U.S. Pat. Nos. 3,622,548, 3,629,212, 3,723,348, 4,168,358,
4,181,790 and 4,361,686. Esters of chlorinated organic acids are preferred
reactivators for use with the vanadium catalyst systems of this invention.
Especially preferred is butyl perchlorocrotanate.
In the processes that utilize multiple catalysts or multiple catalysts
additions during the course of polymerization, the mix free condition of
the reactor refers to the polymer chains of each individual mode of the
MWD and not to the polymer as a whole.
A preferred multiple catalyst system comprises VCl.sub.4 combined with
VOCl.sub.3 and an alkyl aluminum sesquihalide as a cocatalyst. The
resultant polymer is a bimodal MWD polymer.
The end-capped, star, graft, and block copolymers disclosed in the
previously indicated U.S. Pat. No. 4,540,753 are also suitable for use
with the blends of this invention.
In the process disclosed therein, ethylene propylene polymerizations are
capped by a capping agent having at least one functional group which
permits it to attach to the polymer end chain. Most preferably, the
copolymers upon which the end capping function is performed are EPM
copolymers and EPDM terpolymers, as previously disclosed. Further, prior
to end capping the copolymer is preferably a narrow MWD copolymer.
The polymerization process is most preferably performed:
(a) in at least one mix-free reactor,
(b) using a catalyst system that produces essentially one active catalyst
species,
(c) using at least one reaction mixture which is essentially transfer
agent-free, and
(d) in such a manner and under conditions sufficient to initiate
propagation of essentially all polymer chains simultaneously.
After growing the polymer chains to the desired molecular weight, end
capping agent is fed to add one or more end capping units to the polymer
chain, or to produce a structure grafted by the ethylene alpha-olefin
chains.
It will be understood that, depending upon the desired functionality of the
chains, end capping units which have one or a multiplicity of
functionalities, and which themselves may or may not polymerize, are
introduced into the reactor.
As noted above, the end cap units may have one or more than one
functionality.
Unifunctional end capping units may be selected from the group consisting
of: --CO.sub.2 H (1), --OH (2), --SH (3), --X (4), --C--C--benzene (5),
--C--C--(pyridine) (6), --SO.sub.2 H (7), --SO.sub.3 H (8), and mixtures
thereof, wherein X is a halide selected from the group consisting of
fluorine, chlorine, bromine, and iodine.
The capping agents used prepare the above capping units, as numbered, are:
##STR4##
wherein R.sub.6 through R.sub.11 are selected from the group consisting of
alkyl having 1-30 carbon atoms, saturated or unsaturated, branched or
unbranched, aliphatic, aromatic, cyclic, or polycyclic hydrocarbons;
______________________________________
sulfur and H.sub.2 C.dbd.S
(3)
fluoride, chloride, bromide, iodine,
(4)
and mixtures thereof
styrene (5)
vinyl pyridine (6)
SO.sub.2 (7)
SO.sub.3 (8)
______________________________________
In the case of unsaturated ester and ketone capping agents, ketone and
ester functionality, in addition to hydroxyl functionality, may be
produced.
By way of example only, the following capping units may be used:
acetaldehyde, methyl acetate, and methyl ethyl ketone.
The chains are then used as is, or may be nodularized as disclosed in the
previously indicated U.S. Pat. No. 4,882,406.
In yet another approach, the end cap may be composed of one monomer, or a
polymer chain of the monomers to form a novel composition composed of the
original alpha-olefin chain which is coupled to the monomer or polymer
chain, i.e., a raft copolymer. Where the functional group is incorporatd
as a polymer, the polymer itself may be formed prior to or after being
linked to the original polymer.
In this embodiment the functional group may be incorporated as a polymer
unit selected from the group consisting of:
##STR5##
the monomers thereof, and mixtures thereof; wherein R.sub.1 through
R.sub.4 are selected from the group consisting of: alkyl having 1-30
carbon atoms, saturated or unsaturated, branched or unbranched, aliphatic,
aromatic, cyclic, or polycyclic hydrocarbons, and R.sub.5 is the same as
R.sub.4 but may additionally be hydrogen, and wherein x=1-10,000.
Specific compounds include: polycylacrylate, polymethylvinylketone, and
polystyrene.
The process of the invention used to end cap with the above monomers or
polymers comprises reacting the growing chain, respectively, with the
following capping agents:
##STR6##
Specific compounds include: decylacrylate, methylvinyl ketone, styrene,
vinyl pyridine, vinyl acetate, methyl vinyl ether, and methyl
methacrylate.
End capping with any of the above agents (1)-(7) may be performed by
injecting the capping agent into the polymerization reactor to quench
further ethylene alphaolefin Ziegler-Natta polymerization, after which the
end capping reagent itself may be polymerized to form a block copolymer.
For further polymerization to occur in this fashion the catalyst used in
the original polymerization must be capable of polymerizing the agent by
some mechanism, either anionic, radical, cationic, or coordination.
This additional polymerization of the agent may be formed in the same
reactor, or in a different reactor.
As previously stated, end capped copolymers are suitable for blending with
plastics compositions. Moreover, they may be employed as compatiblizers in
blends of EPM and EPDM copolymers with plastic compositions, especially
engineering resins, such as nylons, polycarbonates, polyesters, acetals,
and polyphenylene oxides. When used for such purposes, they are preferably
present in such blends at up to approximately 80 percent by weight of the
blend.
The end capping group may be polymeric, in which case star shaped or graft
polymers may be formed. These polyfunctional end capping groups may be
selected from the group of copolymers consisting of: copolymers of
ethylene and vinylacetate (1); ethylene and acrylic acid esters (2); vinyl
acetate and fumaric acid esters (3); styrene and maleic acid esters (4);
olefins and maleic acid esters (5); homopolyacrylates (6); and epoxidized
natural rubber (7).
The nodular copolymers disclosed in the previously indicated U.S. Pat. No.
4,882,406 are also suitable for use with the blends of this invention.
These nodular copolymers comprises ethylene, at least one alpha-olefin
monomer, and a non-conjugated diene copolymer. Prior to coupling, the
individual polymer chains of the nodular copolymer have at least one
segment that contains only ethylene and the alpha-olefin, and a second
segment that contains ethylene, the alpha-olefin, and the non-conjugated
diene. Prior to the formation of the nodular branched copolymer the
copolymer is a narrow MWD copolymer, as defined herein.
The processes for preparing these nodular copolymers are most preferably
carried out:
(a) in at least one mix-free reactor,
(b) using a catalyst system that produces essentially one active catalyst
species,
(c) using at least one reaction mixture which is essentially transfer
agent-free, and
(d) in such a manner and under conditions sufficient to initiate
propagation of essentially all polymer chains simultaneously.
To form the nodular copolymers, the polymer chains formed in the
polymerization are coupled by reacting the residual double bonds, in the
non-conjugated diene in one polymer chain, with similar double bonds in
other chains. The coupling reaction can be catalyzed by either Ziegler,
cationic, free radical catalysts, or olefin coupling agents.
The preferred reactor for preparing these copolymers is a tubular reactor.
When polymerizing in a tube, the ethylene and propylene are fed to the
reactor inlet along with a suitable Ziegler catalyst. The catalyst is
preferably chosen so that it produces essentially one active catalyst
species. Also, chain transfer reactions during the polymerization must be
minimized. It is well known that ethylene is much more readily polymerized
than propylene. Consequently, the concentration of monomer changes along
the tube in favor of propylene as the ethylene is depleted. The result is
copolymer chains which are higher in ethylene content in the chain
segments grown near the reactor feed inlet and higher in propylene in the
segments grown near the reactor outlet. The resulting chain is
intramolecularly heterogeneous. The extent of heterogeneity in
ethylene/propylene compositions can be moderated somewhat by feeding
additional ethylene at points along the reactor to keep the
ethylene/propylene monomer ratio at a more constant value. An object is to
produce chains with a minimum of interchain compositional variation in
order to assure uniform coupling. This is accomplished by utilizing a
Ziegler catalyst that forms essentially one active catalyst species,
minimizing chain transfer reactions initiating propagation of essentially
all chains simultaneously, and conducting the polymerization such that the
major portion of the catalyst remains active for the entire length of time
that polymerization is occurring in the reactor. The tubular reactor is
also operated at conditions such that the copolymer chains have a narrow
MWD characterized by at least one of the ratios of M.sub.w /M.sub.n and
M.sub.z /M.sub.w being less than 2.0 and 1.8, respectively, prior to
coupling.
In one embodiment, polymerization of the ethylene and propylene is
initiated at the reactor inlet and continued until a first polymer segment
forms comprising at least 50% of the weight of the total polymer to be
produced. Additional monomer feed is then added to the tube consisting of
non-conjugated diene, either alone or in combination with the other
monomer and/or solvent. At the point of nonconjugated diene addition, at
least 50% of the ultimate aniticipated mass of the polymer should have
been formed. A second chain segment is then formed with a non-conjugated
diene content of at least .1 mole 1% and with a M.sub.w value of at least
2000. If the first polymer segment is formed as a series of discontinuous
segments, the first segment shall be considered to include the segments as
a whole for definitional purposes.
Several techniques are available for producing the nodular branched polymer
of this invention. If the nonconjugated diene has both double bonds
polymerizable by the Ziegler catalyst, branching will occur simultaneously
with polymerization in the reactor. In this case the polymer exiting the
reactor will be the final product.
If coupling is to be catalyzed cationically, the cationic catalyst can
either be added to the tubular reactor, to carry out the coupling in the
reactor, or to the polymer product exiting the reactor so that the
coupling can be carried out in a separate process step. Free radical
coupling catalysts are normally Ziegler catalyst poisons and will not
perform at polymerization conditions. In this case, the coupling agent
must be added, and the coupling performed, subsequent to the
polymerization Olefin cross-linking ageants may also be used in a similar
manner.
As already noted, the first copolymer segment in accordance with the
present invention is comprised of ethylene and at least one other
alpha-olefin. It is believed that such alpha-olefin could include those
containing 3 to 18 carbon atoms, e.g., propylene, butene-1, pentent-1,
etc. Alpha-olefins of 3 to 6 carbons are preferred due to economic
considerations. The most preferred alpha-olefin in accordance with the
present invention is propylene.
The diene monomers suitable for use in the practice of this invention by
which the narrow MWD polymers prepared by this invention are coupled, are
of two types: (1) nonconjugated dienes capable of being Ziegler catalyst
polymerized via both double bonds; and (2) the nonconjugated dienes of the
type used to prepare EPDM where the non-conjugated dienes has only one
Ziegler catalyst polymerizable double bond, and the other bond is
cross-linkable by cationic or free radical catalysts, or by olefin
cross-linking agents.
Typical of the coupling agents that can be used to produce the second
terpolymer segment of the chain are the following non-limiting examples:
a) straight chain acyclic dienes such as: 1,4-hexadiene; 1,6-octadiene;
b) branched chain acyclic dienes such as: 5-methyl-1, 4-hexadiene;
3,7-dimethyl-1, 6-octadiene; 3,7-dimethyl-1, 7-octadiene and the mixed
isomers of dihydromyrcene and dihydroocimene;
c) single ring alicyclic dienes such as: 1,4-cyclohexadiene;
1,5-cyclooctadiene; and 1,5-cyclododecadiene;
d) multi-ring alicyclic fused and bridged ring dienes such as:
teetrahydroindene; methyltetrahydroindene; dicyclopentadiene;
bicyclo-(2,2,1)-hepta-2,5 diene; alkenyl, alkylidene, cycloalkenyl and
cycloalkylidene norbornenes such as 5-methylene-2norbornene (MNB),
5-ethylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene; and
5-cyclohexylidene-2-norbornene.
Illustrative, non-limiting examples of the diene monomers coupled by
Ziegler copolymerization catalysts to prepare the nodular polymers of this
invention are norbornadiene, vinyl norbornene and butenyl norbornene.
Illustrative of the dienes coupled by cationic cross-linkable catalyst to
prepare the nodular polymers are 1,4-hexadiene, ENB, and dicylopentadiene.
Illustrative of the dienes coupled by free radical catalysts are MNB, VNB,
and 1,5-hexadiene. Additionally, olefin cross-linking agents may be used.
Such agents include sulfur dichloride, dusulfenyl halides, borane,
dithioalkenes, and mixtures thereof. Of the non-conjugated dienes
typically used to prepare these copolymers, dienes containing at least one
of the double bonds in a strained ring are preferred. The amount of diene
(mol basis) in the diene-containing segment of the polymer could be from
about 0.1% mole to 50%, with 1% to 30% being preferred. The most preferred
range is 2%-20%.
The average ethylene content of the polymer could be as low as about 10% on
a weight basis. The preferred minimum is about 25%. A more preferred
minimum is about 30%. The maximum ethylene content could be about 90% on a
weight basis. The preferred maximum is about 85%, with the most preferred
being about 80%. The ethylene content of the two segments comprising the
polymer can be the same or different. If different, the preferred
composition range for each segment is the same as stated above for the
whole polymer.
The molecular weight of copolymer made in accordance with the present
invention can vary over a wide range. It is believed that the weight
average molecular weight could be as low as about 2,000. The preferred
minimum is about 10,000. The most preferred minimum is about 20,000. It is
believed that the maximum weight average molecular weight could be as high
as about 12,000,000. The preferred maximum is about 1,000,000. The most
preferred maximum is about 750,000. The preferred minimum molecular weight
for an ethylene-propylene copolymer chain segment is 2.times.10.sup.4. For
the ethylene-propylene-non-conjugated diene chain segment the preferred
minimum MW is 2.times.10.sup.3.
In one embodiment, the nodular copolymer is prepared by beginning the
polymerization of the poly co-(ethylene-proplene) which is permitted to
grow to a molecular weight of several tens of thousands, e.g., 10,000 to
50,000 number average molecular weight. The polymerization of the
copolymer will generally have proceeded to about 50% of the total
anticipated weight of polymer at the end of polymerization, more
preferably at least 70% of the total weight; at that point in time, the
diene monomer, and optionally, a cationic catalyst if the diene is subject
to cationically catalyzed coupling are introduced into the reactor with or
without additional ethylene and propylene. With Ziegler copolymerizable
dienes the polymer copolymerizes with the double bonds of the diene
monomer to form the nodular polymers of this invention. This diolefin
copolymerizes at the chain ends couling several chains. Alternatively,
coupling agent may be added at the entrance to the tubular reactor with a
part of the ethylene and alpha-olefin monomer, polymerization being
carried out until nodules are formed and the coupling agent is
substantially converted; then additional ethylene and alpha-olefin are
added to grow nodular polymers of this invention.
These copolymers may be statistical (random) or segmented copolymers
comprising ethylene, alpha-olefin, and halogen-containing monomer which is
an olefinic hydrocarbon chlorosilane or an olefinic halide. The segmented
copolymer may be in nodular form.
These copolymers may further be in the form of graft and clock polymers
formed from the copolymer chains.
The olefinic chlorosilane has the formula
SiRR'.sub.x Cl.sub.3-x
wherein x is in the range of 0-2, R is a Ziegler copolymerizable olefin,
and R' is a hydrocarbon with 1-30 carbon atoms selected from the group
consisting of saturated or saturated as well as branched or unbranched
aliphatic, aromatic, cyclic, and polycyclic hydrocarbons. R may further be
selected from the group consisting of norbornenyl, dicyclopentenyl, and
1-hexenyl. The chlorosilane may further be selected from the formula
CH.sub.2 =CH--(CRR').sub.n --SiR.sub.x Cl.sub.3-x
wherein x is in the range of 0-2, n is greater than or equal to 0, and R
and R' are the same or different, each being a hydrocarbon with 1-30
carbon atoms selected from the group consisting of saturated or
unsaturated as well as branched or unbranched aliphatic, aromatic, cyclic,
and polycyclic hydrocarbons. In a preferred embodiment, the chlorosilane
is selected from the group consisting of vinyl dimethyl chlorosilane,
vinyl ethyl dichlorosilane, 5-hexenyldimethylchlorosilane,
5-hexenyltrichlorosilane, 7-octenyltrichlorosilane, and phenyl
allyldichlorosilane.
The olefinic hydrocarbon halide has the formula
RR'X
wherein
i) R is a Ziegler copolymerizable olefin;
ii) R' is a hydrocarbon with 1-30 carbon atoms selected from a group
consisting of the saturated or unsaturated as well as branched or
unbranched aliphatic aromatic, cyclic, and polycyclic hydrocarbons; and
iii) X is a halogen.
Then preferred olefinic hydrocarbon halides are 5-parachloromethyl
phenyl-2-norbonene and 5-chloromethyl-2-norbonene.
These copolymers are prepared by a polymerization process conducted:
(a) in at least one mix-free reactor,
(b) using a catalyst system that produces essentially one active catalyst
species,
(c) using at least one reaction mixture which is essentially transfer
agent-free, and
(d) in such a manner and under conditions sufficient to initiate
propagation of essentially all polymer chains simultaneously.
A tubular reactor is preferred for the process.
The composition of the copolymer is dependent upon the point at which the
various reactants are added to the reactor. In a tubular reactor, the
statistical polymer will result if the halogen-containing monomer is added
at the reactor inlet and is present along essentially the entire length of
the reactor. The segmented copolymer will result if the halogen-containing
monomer is instead added at one or more location sites along the reactor
with additional ethylene and alpha-olefin appropriately fed; the copolymer
chains will bear second segments corresponding to such locations where the
olefinic chlorosilane or olefinic hydrocarbon halide is added.
The copolymer chains can be cross-linked at their chlorosilane or olefinic
halide functional groups. Where the third compound in the copolymer is an
olefinic chlorosilane, the cross-linking agent is water or at least one
polyfunctional proton donors. Where the halogen-containing monomer is
olefinic hydrocarbon halide, the cross-linking agent is zinc oxide or a
polyfunctional nucleophile.
The structure of the resulting cross-linked copolymer is also dependent
upon the sequence of monomers along the copolymer chains. Where the
olefinic chlorosilane or olefinic hydrocarbon halide has been introduced
at the reactor inlet, and the olefinic chlorosilane or olefinic
hydrocarbon halide is present throughout the chain, cross-linking will
accordingly occur throughout the chain. Where the olefinic chlorosilane or
olefinic hydrocarbon halide is rather introduced at one or more locations
along the reactor, at such addition rates which will cause the formation
of copolymer chains having contiguous first and second segments of
sufficient length, cross-linking will result in nodular regions of second
segments with first segments extending therefrom.
Variations of such nodular copolymer products can be prepared by adding
polyfunctional proton donors or polyfunctional nucleophiles which contain
additional functional groups. Examples of such functional groups are
amides, pyridines, polycaprolactones, pyrrolidone, imidazole,
polycaprolactams, etc.
These copolymers can also be used to make block and graft polymers,
including compatibiliserz and thermoplastic elastomers.
In one embodiment the copolymer chains are reacted with a metalating agent,
such as a branched alkyl lithium. An anionically polymerizable monomer is
then added, which polymerizes anionically to give chains of the monomer
grafted onto the ethylene-alpha-olefin copolymer chains.
The halogen-containing monomer copolymers, upon mixing with certain
plastics, will chemically link with such plastics through the olefinic
chlorosilane or olefinic hydrocarbon halide.
Where the halogen-containing monomer is olefinic chlorosilane, the polymer
will react with polycarbonates, polyamides, polyesters, polyephenylene
oxides, and acetals. The plastic reacts with the polymer to form a
siliconplastic bond, releasing hydrogen from the plastic and halogen from
the olefinic chlorosilane.
Where the halogen-containing monomer is olefinic hydrocarbon halide, the
copolymer will react with polyamides (nylons). The NH.sub.2 group of the
polyamide reacts with the olefinic-hydrocarbon halide. Here too, hydrogen
is released from the plastic and halogen from the halogen-containing
monomer.
In another embodiment a cationic catalyst, such as a Lewis acid, is reacted
with the hydrocarbon halogen functionality on the copolymer chains, and a
cationically polymerizable monomer is then added to graft onto the
copolymer chains.
Among the plastic compositions which can be used in the blend of this
invention are thermoplastic compositions. Suitable thermoplastic
compositions include polypropylenes, polyethylenes, including high density
polyethenes, low density polyethylenes, and linear low density
polyethylenes, polystyrenes, polyvinyl chlorides, polycarbonates,
polyamides (nylons), polyesters, polyphenylene oxides,
ethylene/methylacrylate copolymers, polybutylenes, polyvinyl acetates,
ethylene/vinyl acetate copolymers, polymethyl methacrylates,
acrylonitrile-butadienne-styrenes, acetals, alkyds, acrylics, polyethyl
methacrylates, and heteroblock propylene-ethylene copolymers.
Polypropylene, particularly that having greater than 90% hot heptane
insolubles and melt flow rates of 0.2 to 100, especially 4 to 20 b/10
minutes, are particularly preferred for use with the compositions of this
invention.
One or more of such plastic compositions can be used together. A preferred
combination is that of polypropylene and polyethylene.
Additional suitable plastic compositions are heteroblock propylene-ethylene
copolymers. These copolymers, known in the art, are block or random
thermoplastic copolymers, as opposed to the COZEWITH et al. elastomer
compositions used in the blends of this invention. These block copolymers
contain at least 50% by weight polypropylene, and may further be described
as crystalline heteroblock copolymers having a crystalline melting point
greater than 150.degree. C.
These block copolymers may be prepared by means of a sequential
polymerization. In one such process, wherein the polypropylene is prepared
in a first reactor and transmitted to a second reactor, wherein ethylene
and propylene are added to produce the copolymer. Examples of reactions
for making these block copolymers are shown in HOLZER et al., U.S. Pat.
No. 3,262,992, and CASTAGNA, U.S. Pat. No. 3,937,758.
At least 50% by weight of the polypropylene in these block copolymers is
present as isotactic polypropylene, which provides the thermoplastic
character to these polymers.
The blends of this invention can also include fillers, stabilizers,
antioxidants, processing aids, colorants, and other known additives, if
desired, in conventional amounts.
Preferred plastic compositions for the blends of this invention are
polypropylene and heteroblock propylene-ethylene copolymer. Polyethylene,
such as low density polyethylene (LDPE), linear low density polyethylene
(LLDPE), or high density polyethylene (HDPE) can further be included in
the blend.
The blends of the invention may be prepared by any conventional means. The
blending is generally conducted at a temperature above the melting point
of the plastic, usually at 150.degree. C. or higher. Conventional mixing
apparatus such a Banbury Batch Mixer, a Farrel Continuous Mixer, a single
screw extruder, or a double screw extruder may be employed. Kneading or
roller milling of the blend may also be utilized.
The time required for mixing depends upon the quantity of components in the
blend and the type of mixing apparatus; generally, no more than a few
minutes is required.
At the temperature and shear rate at which the blend is being produced, the
rates of the viscosity of the elastomer of the invention to the viscosity
of the polypropylene should be less than approximately 4.0, preferably
approximately 0.3 to approximately 3.0. This will give an intimate
dispersion of the elastomer in the plastic.
For the purpose of obtaining the desired viscosity ratio, the viscosity of
the elastomer and propylene at the shear rate and temperature of the
mixing apparatus can be estimated by a constant rate capillary rheometer,
such as the Monsanto Processability Tester (MPT).
With these data, it is therefore possible to select a suitable combination
of the two components such that the viscosity of the elastomer, under the
appropriate temperature and shear rate conditions, is approximately 0.3 to
4.0 times, preferably approximately 0.3 to 3.0 times, that of the
polypropylene in which it is to be dispersed.
Subsequent to the blending step, the blends can be molded in any
conventional molding equipment, such as injection molding machines or
extruders, utilizing molding cycles, temperatures, and pressures which
will bring about the desired shape and thickness of the molded article.
Generally, injection molding may take place at temperatures in the range of
approximately 174.degree.-315.degree. C. for 05-10 minutes or more, and
injecting into a room-temperature mold at 500 to 3,000 psi, depending upon
the desired shape and thickness of the molded article.
The elastomer of the blends of the invention, and the polyethylene, when
present, can be cured after blending, and during or prior to the molding
step.
Curing may be performed by adding to the blend an amount of a curing agent,
such as a free radical generating or crosslinking agent, sufficient to
cause substantially complete crosslinking of these cross-linkable
components, and subjecting them to curing conditions, e.g., a temperature
in the range of approximately 175.degree.-205.degree. C.
Organic peroxides are suitable for use as curing agents. Examples of useful
organic peroxides include dicumal peroxide, di-tertiary butyl peroxide,
tert-butyl perbenzoate, bis (a,a-dimethylbenzyl) peroxide, 2, 5-bis
(tert.-butylperoxy)-2,5-dimethylhexane, a, a' bis (tert.butylperoxy)
diisopropylbenzene, and others containing tertiary carbon groups, to name
a few. Mixed peroxide-filler type curing systems or packages may also be
employed if desired, such as Vulcup R 40 KE, sold by Hercules
Incorporated, which is comprised about 40 wt.% a,a-bis(t-butylperoxy)
diisopropylbenzene on Burgess KE clay. Another example of a suitable
peroxide-filler cure package includes Dicup R 40 KE, which contains 40
wt.% dicumyl peroxide on Burgess KE clay, also sold by Hercules
Incorporated.
Phenolic curatives and cure activators are also suitable as curing agents.
The particular amount of curing agent required to provide full curing is
well known in the art, and may be readily determined by reference to
appropriate literature provided by Hercules Incorporated, Wilmington, Del.
By way of example, an organic peroxide is generally used in amounts of
from about 0.5 to about 4 parts, preferably from about 1 to about 3 parts,
per 100 parts of cross-linkable rubber and polyethylene.
Triallylcyanurate is preferably incorporated into the mixture prior to
curing, for the purpose of enhancing the curing and preventing degradation
of the plastic composition.
Where the plastic compositions of the blends of the invention comprise
polypropylene and polyethylene, the polypropylene generally comprises at
approximately 70-95% by weight of the blend; the polyethylene, 2-20%; the
elastomer composition, 2-28%.
Where polypropylene and polyethylene are employed, the elastomer
compositions of the blends of the invention may be preblended with the
polyethylene prior to blending with the polypropylene.
When the composition of the invention comprises approximately 50% by weight
or more, preferably up to approximately 80%, and, most preferably, up to
approximately 75% by weight, of the elastomer, and approximately 50% or
less by weight poplypropylene, subjecting the composition to the
previously disclosed curing step will result in a product known as a
thermoplastic elastomer. Such a product exhibits both thermoplastic and
elastomeric properties, i.e, the product will process like a
thermoplastic, but have physical properties like elastomers. Shaped
articles can be formed from such a product by extrusion, injection molding
or compression molding without requiring vulcanization.
The previously indicated elastomeric compositions disclosed in the COZEWITH
et al. patent and related patents and applications can be employed in the
techniques discussed in Coran et al., U.S. Pat. No. 4,130,535 and
Abdou-Sabet et al., U.S. Pat. No. 4,311,628, the disclosures of which are
hereby incorporated by reference thereto, to prepare the thermoplastic
elastomers of the invention.
Where the plastic composition of the blend of the invention is primarily
polypropylene comprising approximately 90% or more by weight of the blend,
and the elastomer composition is primarily single mode narrow MWD
copolymer comprising approximately 10% or less by weight of the blend, the
blend will comprise a continuous phase of the polypropylene with a
discontinuous phase of narrow MWD copolymer dispersed therein. As the
proportion of narrow MWD copolymer in the blend is increased above 10% by
weight of the blend, at some point the continuous-discontinuous phases
configuration of the blend will transform into a cocontinuous phases
configuration.
Where polyethylene is also present, and the polypropylene comprises
approximately 85% or more by weight, of the blend, with the polyethylene
comprising approximately 5% or less and the single mode narrow MWD
copolymer comprising approximately 10% or less by weight of the blend, the
blend will also assume a continuous-discontinuous phase configuration; the
discontinuous phase will be in the form of particles having an inner
region of polyethylene and an outer surface of narrow MWD copolymer.
The presence of the elastomer composition compatibilizes the polyethylene
and polypropylene by rendering the blending of these two plastic
compositions easier.
Various properties for certain narrow MWD copolymers suitable for use with
the blends of this invention are shown in Table I.
TABLE I
______________________________________
Characteristics of Copolymers
Wt. % M(.sub.L 1 + 8,
Wt. %
Polymer
Ethylene 127.degree. C.
Diene.sub.(1)
-- M.sub.w
-- M.sub.w /-- M.sub.n
______________________________________
A 39.0 40 0 190,000
1.4
B 47.0 40 0 176,000
1.4
C 65.0 15 0 140,000
1.5
D 65.0 50 0 140,000
1.4
E 50.0 28 5.0 100,000
1.5
F 73.0 75.0 5.3 -- --
______________________________________
.sub.(1) 5ethylidene-2-norbornene
The composition and properties of two blends, both employing a 5 MFR
polypropylene homopolymer, one further employing an elastomer known in the
art and the other employing a narrow MWD copolymer of the invention, are
listed in Table II.
TABLE II
______________________________________
Evaluation of Elastomer Blended
With a MFR Polypropylene Homopolymer
Sample No.
1 (Control)
2
______________________________________
Composition
Vistalon 503.sup.(1) wt. % (grams)
10.05 (1273) --
Polymer B, wt. % (grams)
-- 10.05
(1273)
Polyethylene.sup.(2) wt. % (grams)
4.93 (624) 4.93 (624)
Polypropylene.sup.(3) wt. % (kilograms)
85.0 (10.8) 85.0 (10.8)
Irganox 1076, wt. % (grams)
0.02 (3) 0.02 (3)
Mechanical Properties
Melt Flow Rate @ 230.degree. C.,
4.3 4.8
g/10 min.
Izod Impact Strength, ft.-lb./in.
21.degree. C., notched
1.2 1.0
-18.degree. C., notched
0.57 0.54
-30.degree. C., unnotched
10.1 9.7
-30.degree. C., unnotched knit line
2.1 2.6
Gardner Impact Strength, in.-lb
-18.degree. C. 135 138
-30.degree. C. 112 126
Flexural Modulus, secant,
160.1 161.3
psi .times. 10.sup.-3
Tensile Strength @ break, psi
3678 3978
Knit line Tensile, psi
2385 2783
______________________________________
.sup.(1) Exxon Chemical Americas EPM: Mooney Viscosity (M.sub.L 1 + 8'
@127.degree. C.) = 30; 49 wt % ethylene
.sup.(2) 0.3 MI, 0.95 g/cc density
.sup.(3) Polypropylene MFR = 5
The composition and properties of three blends, all employing a 12 MFR
polypropylene homopolymer while each of the other two employs a narrow MWD
copolymer of the invention, are comparatively listed in Table III.
TABLE III
__________________________________________________________________________
Evaluation of Elastomer Blended with
12 MFR Polypropylene Homopolymer
Sample No.
3
(Control)
4 5
__________________________________________________________________________
Composition
Vistalon 503.sup.(1), wt. % (grams)
6.7
(2010)
Polymer A, wt. % (grams)
-- 6.7
(2010)
--
Polymer B, wt. % (grams)
-- -- 6.7
(2010)
Polyethylene.sup.(2) wt. % (grams)
3.28
(984)
3.28
(984)
3.28
(984)
Polypropylene.sup.(3), wt. % (kg)
90.0
(27)
90.0
(27)
90.0
(27)
Irganox 1076, wt. % (grams)
0.02
(6) 0.02
(6) 0.02
(6)
Mechanical Properties
Melt Flow Rate @ 230.degree. C.
9.2 9.6 9.6
g/10 min.
Izod Impact Strength, ft.-lb./in.
21.degree. C., notched
0.70 0.62 0.55
-18.degree. C., notched
0.44 0.41 0.43
-30.degree. C., unnotched
6.4 6.5 6.3
-30.degree. C., unnotched knit line
1.8 1.8 2.7
Flexural Modulus, secant,
160.1 161.3
psi .times. 10.sup.-3
Gardner Impact Strength, in.-lb
-18.degree. C. 71 83 80
-30.degree. C. 45 78 74
Tensile Strength @ break-psi
4552 4680 4633
Knit line Tensile, psi
2622 2785 3655
__________________________________________________________________________
.sup.(1) Exxon Chemical Americas EPM: Mooney Viscosity (M.sub.L 1 + 8'
@127.degree. C.) = 30; 49 wt % ethylene
.sup.(2) 0.3 MI, 0.95 g/cc density
.sup.(3) Polypropylene MFR = 12
The composition and properties of 5 additional blends, all employing a 15
MFR polypropylene homopolymer, one further employing an elastomer known in
the art and the others each further employing a narrow MWD copolymer of
the invention, are comparatively listed in Table IV.
TABLE IV
__________________________________________________________________________
Evaluation of Elastomer Blended with
15 MFR Polypropylene Homopolymer
Sample No.
6
(Control)
7 8 9 10
__________________________________________________________________________
Composition
Vistalon 503.sup.(1) wt. % (kg)
10.05 (8.5)
-- -- -- --
Polymer B, wt. % (kg)
-- 10.05 (8.5)
-- -- --
Polymer C, wt. % (kg)
-- -- 10.05 (8.5)
-- --
Polymer D, wt. % (kg)
-- -- -- 10.05 (8.5)
--
Polymer E, wt. % (kg)
-- -- -- -- 10.05 (8.5)
Polyethylene.sup.(2) wt. %
4.93 4.93 4.93 4.93 4.93
(kg) (4.18) (4.18) (4.18) (4.18) (4.18)
Polypropylene.sup.(3) wt. % (kg)
85.0 85.0 85.0 85.0 85.0
(kg) (72.0) (72.0) (72.0) (72.0) (72.0)
Irganox 1076, wt. %
0.02 0.02 0.02 0.02 0.02
(kg) 0.02 (0.02) (0.02) (0.02) (0.02)
Mechanical Properties
Melt Flow Rate @ 230.degree. C.
10.9 10.5 14.9 10.6 11.5
g/10 min.
Izod Impact Strength, ft. lb./in.
21.degree. C., notched
0.76 0.77 0.63 0.65 0.76
-18.degree. C., notched
0.44 0.54 0.34 0.35 0.53
-30.degree. C., unnotched
6.0 6.9 4.8 4.2 7.8
-30.degree. C., unnotched knit line
1.8 2.7 3.1 2.2 2.2
Gardner Impact Strength, in.-lb
-18.degree. C. 62 88 15 30 146
-30.degree. C. 56 66 8 18 121
Flexural Modulus secant,
168.9 174.3 162.3 187.5 175.1
psi .times. 10.sup.-3
Ten. Strength @ break, psi
2367 2419 1890 2744 2382
Knit line Tensile, psi
3320 3410 2052 3620 2540
__________________________________________________________________________
.sup.(1) Exxon Chemical American EPM: Mooney Viscosity (M.sub.L 1 + 8'
@127.degree. C.) = 30; 49 wt % ethylene
.sup.(2) 0.3 MI, 0.95 g/cc density
.sup.(3) Polypropylene = 15 MFR
TABLE V
__________________________________________________________________________
Evaluation of Narrow MWD copolymer in Thermoplastic
Olefin (TPO) Formulations
Sample No.
11 12 13 14 15
__________________________________________________________________________
Composition
Vistalon 503.sup.(1) wt. % (g)
25.0 (375)
-- -- -- --
Vistalon 7000.sup.(2) wt. % (g)
-- 25.0 (375)
-- -- --
Polymer F, wt. % (g)
-- -- 25.0 (375)
-- --
Polymer C, wt. % (g)
-- -- -- 25.0 (375)
--
Polymer D, wt. % (g)
-- -- -- -- 25.0 (375)
Polypropylene,.sup.(3) wt. %
74.8 74.8 74.8 74.8 74.8
(g) (1122) (1122) (1122) (1122) (1122)
Irganox 1076, wt. % (g)
0.2 (3) 0.2 (3) 0.2 (3) 0.2 (3) 0.2 (3)
Mechanical Properties
Melt Flow Rate @ 230.degree. C.,
3.55 2.45 2.54 4.51 3.80
g/10 min
Spiral Flow.sup.(4), cm
15.6 14.6 12.5 15.2 14.8
Izod Impact Strength, ft-lb/in
21.degree. C., notched
10.1 7.9 2.0 4.0 7.3
-20.degree. C., unnotched
28.4 24.9 21.1 13.8 15.0
30.degree. C., unnotched
-- -- 16.3 12.9 13.7
40.degree. C., unnotched
-- -- 10.3 9.0 11.0
Ten. Strength @ Break-psi
2510 2510 1920 2220 2330
Elongation @ Break, %
300 290 145 210 170
Flexural Modulus,
120 125 129 116 120
psi .times. 10.sup.-3
__________________________________________________________________________
.sup.(1) Exxon Chemical Americas EPM: Mooney Viscosity (M.sub.L 1 + 8' @
127.degree. C.) = 30; 49 wt. % ethylene
.sup.(2) Exxon Chemical Americas EPDM: Mooney Viscosity (M.sub.L 1 + 8' @
127.degree. C.) = 55; 70 wt. % ethylene; 5 wt. % ENB
.sup.(3) Polypropylene MFR = 5.0
.sup.(4) Nonstandard test for comparison purposes; higher values indicate
better mold filling characteristics. Conditions using Boy laboratory
injection press: Pressure = 800 psi; barrel temperature 230.degree. C.;
nozzle temperature 267.degree. C.; mold at 53.degree. C.; 13 second
injection; 20 second hold
TABLE VI
______________________________________
Thermoplastic Olefins (TPO's) Containing
Marrow MWD Copolymer Plus Talc
Sample No.
Composition 16 17 18
______________________________________
Polymer C, wt. % (g)
31.0 (465)
30.0 (450)
28.0 (420)
Mistron Vapor, wt. % (g)
5.0 (75)
10.0 (150)
15 (225)
Heteroblock propylene-ethylene
63.8 (957)
59.8 (897)
56.8 (852)
copolymer.sup.(1) wt. % (g)
Irganox 1076 wt. % (g)
0.2 (3) 0.2 (3) 0.2 (3)
______________________________________
.sup.(1) Hetero block propyleneethylene copolymer is a 15 MFR polymer
containing 88 percent by weight of a polypropylene block and 12 percent b
weight of a postblock of a copolymer of ethylene and propylene, the
postblock containing 40 weight percent ethylene.
The following examples more particularly illustrate the nature of the
invention but are not intended to be limitative thereof. In the following
examples, the mechanical property evaluations were made employing the
following tests.
______________________________________
TEST FOR VIA ASTM
______________________________________
Melt Processability
MFR D1238 L
Stiffness Flexural Modulus
D790 I.A.
Stiffness Properties
Tensile & Elongation
D638
at yield and break
Impact Strength
Notched Izod D256, Method A
Unnotched Izod D256, Method A
Gardner Impact D3029
______________________________________
Test specimens for measuring the above mechanical properties were produced
on a Watson Stillman Injection Molding Machine.
EXAMPLE 1
Two impact propylene blends were made and compared for impact properties
and knit line strength. One blend was prepared with a commercially
available ethylene propylene copolymer (Vistalon 503) having a MWD of 4.5.
The other was prepared with Polymer B of Table II.
Each blend was prepared by initially mixing the copolymer and HDPE in a
Banbury Mixer for 4 minutes at a temperature of about 200.degree. C. The
copolymer/HDPE mixture was then pelletized and mixed with a polypropylene
homopolymer in a Banbury Mixer for about 4 minutes at approximately
200.degree.. The mechanical properties of the 2 blends are also set forth
in Table II.
The results of Table II illustrate that incorporation of a narrow MWD
ethylene-propylene copolymer in a 5 MFR polypropylene blend provides
improved knit line properties while maintaining all other properties
approximately constant.
EXAMPLE 2
Impact polypropylene copolymer blends were prepared with narrow MWD
copolymers in accordance with the formulations set forth in Table III. For
purposes of comparison, an impact polypropylene blend was prepared with
Vistalon 503, a commercially available copolymer having a MWD of 4.5.
Each of the blends was prepared by initially mixing the copolymer and HDPE
in a Banbury Mixer for 4 minutes at a temperature of about 200.degree. C.
Each copolymer/HDPE mixture was then cooled and chopped in small squares.
The final impact copolymer blend was prepared by mixing the copolymer/HDPE
mixture with a polypropylene homopolymer in a 2.5 inch Royle extruder. The
die temperature of the extruder was approximately 200.degree. C. The
mechanical properties of these blends are set forth in Table III.
As illustrated, the blends containing the narrow MWD copolymer had improved
impact and knit line properties.
EXAMPLE 3
Impact copolymer blends were prepared with narrow MWD copolymers in
accordance with the formulations set forth in Table IV. As in example 2,
one blend was prepared with Vistalon 503 for comparison purposes.
Each of the blends was prepared in accordance with the procedure set forth
in Example 2. The mechanical properties of the blends are set forth in
Table IV.
As with the narrow MWD blends of Example 2, Samples 7 and 10 had better
impact properties than the Vistalon 503 blend, Sample 6. Furthermore,
Sample 8 had better Izod knit line properties than the control, but lower
Gardner impact properties.
EXAMPLES 4
Five thermoplastic olefins (TPO) were made and compared for mechanical
properties. For comparison purposes, two of the blends were prepared with
commercially available EPM/EPDM elastomers.
Each blend was prepared by mixing the copolymer and polypropylene
homopolymer in a Banbury mixer for about 4 minutes at approximately
200.degree. C. After completing mixing, the copolymer-polypropylene blend
was cooled and granulated. The mechanical properties and polymer
components of all the TPO blends prepared are set forth in Table V.
EXAMPLE A
Three thermoplastic olefins (TPO) are made in accordance with the
formulations set forth in Table VI. Each blend is prepared by mixing the
heteroblock propylene-ethylene block copolymer, mistron vapor and narrow
MWS copolymer in a Banbury mixer for about 4 minutes at approximately
200.degree. C. After completing mixing, the blend is cooled and
granulated.
EXAMPLE B
A moderately filled flexible compound for extrusion, molding and
thermoforming applications is prepared in accordance with the formulation
below:
______________________________________
Polymer C.sup.(1) 23 wt. % (345 grams)
Ethylene/Vinyl Acetate Copolymer
36 wt. % (540 grams)
Flexon 766 oil 10 wt. % (150 grams)
Atomite - C Co.sub.3 30 wt. % (450 grams)
Stearic Acid 0.6 wt. %
(9 grams)
Irganox 1076 0.4 wt. %
(6 grams)
______________________________________
.sup.(1) 2.5 MI; 19% VA
The blend is prepared by mixing Polymer C, ethylene/vinyl acetate
copolymer, Flexon 766 oil and atomite in a Banbury mixer at high rotor
speed until flux (approximately 2 minutes). After flux, the blend is mixed
for another 3 minutes at low rotor speed. Next, the stearic acid and
Irganox 1076 are added to the blend, and the blend is mixed for another
minute at low rotor speed. Finally, the blend is dumped, cooled and
granulated.
EXAMPLE C
An impact polypropylene blend is made by blending 3.4 wt.% (51 grams) of
Polymer C, 1.7 wt.% (26 grams) of a 0.3 MI HDPE, 0.8 wt.% (12 grams) of
Irganox 1076 and 94.1 wt.% (1424 grams) of a 4 MFR heterblock propylene
ethylene copolymer containing 90 percent by weight of a polypropylene
block and 10 percent by weight of a postblock of a copolymer of ethylene
and propylene, the postblock containing 40 weight percent ethylene in a
Banbury mixer for 4 minutes at 200.degree. C. After completing mixing, the
blend is cooled and granulated.
EXAMPLE D
A thermoplastic olefin (TPO) is prepared by mixing 49.5 wt.% (750 grams) of
Polymer C, 9.9 wt.% (150 grams) of Sunpar 2280 oil, 0.99 wt.% (15 grams)
of Irganox 1010 and 39.6 wt.% (600 grams) of a 4 MFR heteroblock propylene
ethylene copolymer containing 88 percent by weight of a polypropylene
block and 12 percent by weight of a postblock of a copolymer of ethylene
and propylene, the postblock containing 40 weight percent ethylene, for
approximately 4 minutes in a Banbury mixer at 200.degree. C. After
completing mixing, the blend is cooled and granulated.
EXAMPLE E
A thermoplastic elastomer is prepared in accordance with the formulation
shown below:
______________________________________
Polymer E 750 grams (50 wt. %)
Profax 6823 PP (0.4 MFR)
251 grams (16.7 wt. %)
Nucap 190 Clay 159 grams 10.6 wt. %)
Titanium Dioxide 21 grams (1.4 wt. %)
Sun-O-Lite 127 21 grams (1.4 wt. %)
Sunpar 150 oil 239 grams (15.9 wt. %)
SP 1045 Resin 44 grams (2.9 wt. %)
ZnO 9 grams (0.6 wt. %)
Stannous Chloride 7.5 grams (0.5 wt. %)
______________________________________
The blend is prepared by mixing Polymer E, Profax 6823 PP, Nucap 190 Clay,
Titanium Dioxide, and Sun-O-Lite 127 in a Banbury Mixer at high rotor
speed until flux (about 2 minutes). After flux, 119.5 grams of the oil is
added and the blend is mixed for 1 minute. Next, the remainder of the oil
is added and the blend is mixed for another minute. With the oil in the
blend, the SP 1045 Resin is added and mixed for 20 seconds. Then, the ZnO
and stannous chloride are added and the blend is mixed for 6 minutes at a
low rotor speed. (Temperature is about 200.degree..) Finally, the blend is
dumped, cooled and granulated.
EXAMPLE F
A thermoplastic elastomer is prepared in accordance with the formulation
shown below:
______________________________________
Polymer E 860 grams (57.3 wt. %)
Profax 6823 PP (0.4 MFR)
251 grams (16.7 wt. %)
Nucap 190 Clay 159 grams (10.6 wt. %)
Titanium Dioxide 21 grams (1.4 wt. %)
Sun-O-Lite 127 21 grams (1.4 wt. %)
Sunpar 150 oil 129 grams (8.6 wt. %)
SP 1045 Resin 44 grams (2.9 wt. %)
ZnO 9 grams (0.6 wt. %)
stannous chloride 7.5 grams (0.5 wt. %)
______________________________________
The blend is prepared by mixing Polymer E, Profax 6823 PP, Nucap 190 Clay,
Titanium Dioxide, and Sun-O-Lite 127 in a Banbury Mixer at high rotor
speed until flux (about 2 minutes). After flux, the oil is added the blend
is mixed for 1 minute. Next, the SP 1045 resin is added and the blend is
mixed for another 20 seconds. Then, the ZnO and Stannous Chloride are
added and the blend is mixed for 6 minutes at a low rotor speed.
(Temperature is about 200.degree..) Finally, the blend is dumped, cooled
and granulated.
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